In the name of God the Merciful the Compassionate

Transcription

IICC12
In the name of God the Merciful the Compassionate
IICC12
IICC12
Preface
The 12th Iranian Inorganic Chemistry Conference (IICC12) took place at the University of Guilan,
City of Rasht (Iran) on 15-16 September 2010 (24-25 Shahrivar 1389). It was organized by
Chemistry Department of Guilan University and Iranian Chemistry Society. Shortly after first call,
about 850 abstracts were submitted from all around the country, covering many aspects of modern
inorganic chemistry including synthesis and characterization of new inorganic compounds,
bioinorganic chemistry, organometallic chemistry, kinetics and mechanisms of inorganic reactions,
inorganic polymers, nano chemistry, spectroscopy in inorganic chemistry, catalysis and theoretical
inorganic chemistry.
A scientific committee, composed of 25 reviewers in different fields, peer reviewed the abstracts to
ensure maximum compatibility. This resulted in acceptance of 822 abstracts (60 oral
communications and 762 posters).
I have to thank the members of both executive and scientific committees, in advance. I also,
appreciate the IICC12 organizing committee members. Valuable support of our sponsors is also
gratefully acknowledged.
Finally, I hope you enjoyed both inorganic chemistry and Guilan province with its majestic
landscapes, adorable foods and lovely culture.
Khalil Tabatabaeian
Conference chairman
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IICC12
Conference Chair
Dr. Sadr Momtaz
Vice president of research
Executive Committee
Dr. Fallah Shojaei
Dr. Shabani poor
Dr. Shams Nateri
Dr. Salahi
Dr. Rozati
Dr. Ghalami
Dr. Tabatabaeian
Dr. Khorshidi
Mr. Jahandideh
Mr. Khaleghi
Vice president of education
Dean of faculty of sciences
Director of research department
Director of university's publication office
Deputy of research (faculty of sciences)
Head of chemistry department
President of 12th inorganic chemistry conference
Faculty member of chemistry department
Director of student affairs
Director of the university presidential office
Scientific Committee
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Dr.
Tajarrodi
Momeni
Tarassoli
Keipoor
Mirkhani
Moghadam
Joshaghani
Khavasi
Morsali
Tabatabaeian
Fallah Shojaei
Zanjanchi
Khorshidi
Behzad
Dehghanpoor
Dehghan
Mirzaei
Yadollahi
Hosseini Yazdi
Taiebi
Vafazadeh
Abbasi
Eslami
Nabavizadeh
Mohammadi
University of science and technology
University of Khajeh Nasir e Toosi
Shahid Chamran university of Ahwaz
Bu Ali Sina university
University of Isfahan
Razi University
University of Shahid Beheshti
University of Tarbiat Modarres
University of Guilan
University of Semnan
University of Azzahra
University of Kashan
Industrial university of Shahrood
University of Tabriz
University of Tarbiat Moallem Sabzevar
University of Yazd
University of Tehran
University of Mazandaran
University of Shiraz
University of Khalije Fars
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Organizing Committee members
H. Fallah Moafi
A. Dadashi
M. Loghmani
M. Khoshnood Jalali
M. Ashrafi Islami
E. Haghighi
M. Moghadam
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Invited
Lectures
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"Biomimetic Dyes": Water-soluble Tin (IV) Porphyrins as Photosensitizers for Artificial
Photosynthesis
Philipp Kurz, Imen Righi and Karen Geisel
Institute for Inorganic Chemistry, Christian-Albrechts-University Kiel
Max-Eyth-StraBe 2,24118 Kiel (Germany)
www.ac.uni-kiel.de/phkurz
Light-driven water splitting into hydrogen and oxygen is currently intensely discussed as an option
for the conversion of solar energy into a "solar fuel".[1] The great challenges to make such a
scheme a reality are a) the development of efficient catalysts from abundant resources for water
oxidation and proton reduction and b) the coupling of these catalytic reactions to light-driven redox
processes. For the latter, nature uses chlorophylls (substituted main group porphyrins) as dyes and
takes advantage of the strong absorbance and favourable photochemistry of such compounds [2].
We have synthesized water soluble tin(lV) porphyrins[3] as possible analogues of the P68o/P700
photoreaction centers in the natural photosystems I and II. An example, the complex
Na4[SnIVCl2TPPS] (TPPS=tetrakis(4-sulfonatophenyl)porphyrin), is shown above. Subsequently their
properties were investigated by spectroscopy, electroanalytical methods and fluorescence
quenching experiments. These results, as well as catalysis studies in which the compounds might
be useful as dyes in light-driven water oxidation / proton reduction systems (above, right), will be
presented.
[1] W. Lubitz, E. J. Reijerse, J. Messinger, Energy Environ. Sci. 2008, 1, 15-31.
[2] V. Balzani, A. Credi, M. Venturi, ChemSusChem 2008, 1, 26-58.
[3] S. Wang, K. Enornoto, S. Tanizaki, I. Tabata, K. Hisada, T. Hori, S. Okubayashi, Sen'i
Gakkaishi 2003, 59, 48-52.
ii
IICC12
Heterogeneous catalysts in organic synthesis
Shahram Tangestaninejad
Department of Chemistry, Catalysis Division, Isfahan University, Isfahan 81746-73441, Iran
Application of reusable heterogeneous catalysts has received considerable importance in organic
synthesis because of their environmental, economical and industrial aspects [1]. The development
of efficient methods using recoverable and reusable catalysts is an important goal in organic
chemistry specially in asymmetric synthesis [2]. Up to now, many several reusable and
heterogenous catalysts have been designed and used. Metal colloides, mineral clays and supported
reagents on silica gel, alumina and other solid supports are some common examples of
heterogenous catalysts that have extensive applications in organic transformations [3-5]. These
catalysts have attracted a great deal of attention due to their ease of handling, enhanced reaction
rates, greater selectivity and simple workup in most cases.
Here, we review our recent works on the preparation of new heterogenized homogeneous catalysts
and their applications in organic synthesis.
These catalysts include biomimetic catalysts such as metalloporphyrins and Schiff base complexes,
polyoxometallates and metal carbonyls.
References
[1] (a) S. Tamagaki, R. J. Card, D. C. Neckers, J. Am. Chem. Soc. 100 (1978) 6635; (b) K.
Molvinger, M. Lopez, J. Court, J. Mol. Catal. A: Chemical 150 (1999) 267; (c) C. J. Magesh, R.
Nagarajan, M. Karthik, P. T. Perumal, Appl. Catal. A: General 266 (2004) 1; (d) T. Maki, K. Ishihara,
H. Yamamoto, Org. Lett. 7 (2005) 5043; (e) J. Azizian, A. A. Mohammadi, A. R. Karimi, M. R.
Mohammadizadeh, J. Org. Chem. 70 (2005) 350.
[2] (a) D. A. Annis, E. N. Jacobsen, J. Am. Chem. Soc. 121 (1999) 4147; (b) P. Vachal, E. N.
Jacobsen, Org. Lett. 2 (2000) 867; (c) Y. S. Kim, S. Matsunaga, J. Das, A. Sekine, T. Ohshima, M.
Shibasaki, J. Am. Chem. Soc. 122 (2000) 6506.
[3] A. Roucoux, J. Schulz, H. Patin, Chem. Rev.102 ( 2002) 3757.
[4] (a) G. K. Jnaneshwara, V. H. Deshpande, A. V. Bedekar, J. Chem. Res. (S) (1999) 252; (b) R. S.
Varma, Tetrahedron 58 (2002) 1235; (c) V. Badathala, Synlett (2004) 388.
[5] (a) G. W. Kabalka, R. M. Pagni, Tetrahedron 53 (1997) 7999; (b) H. Kotsuki, T. Shimanouchi, R.
Ohshima, S. Fujiwara, Tetrahedron 54 (1998) 2709; (c) C. Ramesh, G. Mahender, N. Ravindranath,
B. Das, Tetrahedron Lett. 44 (2003) 1465; (d) S. Samajdar, F. F. Becker, B. K. Banik, Tetrahedron
Lett. 41 (2000) 8017.
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i
Towards understanding the structure of polybasic ligands and corresponding metal
complexes in the solution and the solid state via theoretical studies on their
protonation, formation and structure.
Sadegh Salehzadeh
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
For many years chemists have been involved in determination of protonation constants of
polybasic molecules and formation constants of metal complexes. While the macroscopic
protonation constants are reported for many types of polybasic ligands, there are few
measurments for microscopic protonation constants. On the other hand, the most measured
formation constants for the metal complexes of polybasic ligands are those reported for
[ML]n+, [M(HL)](n+1)+ and [ML(OH)](n-1)+ complexes, where Mn+ and L represent the metal ion
and the ligand, respectively. However, in most cases the real/correct formulation of a metal
complex in aqueous solution is not as [ML]n+, [M(HL)](n+1)+ and etc. We note that the solvent
molecules and/or anions, X-, of the initial metal salt (or anions of metal salts used for
increasing the ionic strength) can be easily coordinated to the metal ion. Obviously, chemists
show, schematically, their complexes as [ML]n+, [M(HL)](n+1)+ and etc., because the
experimental determination of exact formulation and/or correct structure for actual species in
solution is not easily possible. However, we note that with the development of computers in
recent years the quantum chemistry has become a powerful tool in the hands of chemists to
solve their problems in both the gas phase and solution. We have been interested in studying
the proton affinity of polybasic ligands and metal complexes and their correlation with the
protonation and formation constants in solution, respectively.1-6 Very recently, we showed that
the study on proton affinities of polybasic molecules and their metal complexes at gas phase is
useful for understanding their structures in solution.5-7 We have also reported a computational
method, capable of predicting reasonably absolute microscopic protonation constant values for
polybasic molecules.8 In addition to above studies that give us good information about the
structure of polybasic molecules and their metal complexes in solution we have also found
good agreements between the gas phase structures of metal complexes and their solid state
structures.9
References:
1- Salehzadeh, S.; Bayat, M. Chem Phys Lett 2006, 427, 455.
2. Salehzadeh, S.; Bayat, M.; Hashemi, M. J Phys Chem A 2007, 111, 8188.
3. Salehzadeh, S.; Bayat, M.; Ward, M. D. J Phys Chem A 2008, 112, 4090.
4. Salehzadeh, S.; Shooshtari, A.; Bayat, M. Dalton Trans 2009, 2865.
5. Salehzadeh, S.; Bayat, M.; Yaghoobi, F. J Mol Struct (THEOCHEM) 2009, 906, 68.
6. Salehzadeh, S.; Yaghoobi, F.; Bayat, M. Chem Phys 2009, 361, 18.
7. Salehzadeh, S.; Bayat, M. J Comput Chem 2010, 31, 2371.
8. Salehzadeh, S.; Gholiee, Y.; Bayat, M. Int. J. Quant. Chem., In press.
9. See for example: Salehzadeh et al, Polyhedron 2005, 24, 1478; J. Mol. Structure 2006, 785, 54;
Polyhedron 2008, 27, 3549; J Coord Chem 2009, 62, 2532; Polyhedron 2010, 29, 850.
IICC12
ORALS
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O-1
Effects of various alcohols on Catalytic Epoxidation of Alkenes by Tetra-n
butylammonium Periodate and (Tetraarylporphyrinato) manganese (III)
Daryoush Mohajer and Massoumeh Abbasi*
Department of Chemistry, Shiraz University, Shiraz 71454, Iran
[email protected]
The epoxidation of cyclooctene and cis-stilbene was performed by tetra-n-butylammonium
periodate (n-Bu4NIO4) in the presence of (tetraarylporphyrinato) manganese (III) [Mn(Por)] and
imidazole (Im) in various CH2Cl2/alcohol solvents {alcohol = CH3OH, C2H5OH, n-C3H7OH, i-C3H7OH,
t-C4H9OH}. In accord with the coordinating abilities of the alcohols to the MnPor, the epoxidation
yields increased from CH2Cl2/CH3OH to CH2Cl2/t-C4H9OH. In the epoxidation of cis-stilbene in the
presence of manganese (III) tetraphenyl-porphyrin acetate [MnTPP(OAc)], the cis- to trans-stilbene
oxide ratio increased consistently with the bulk of the alcohol in CH2Cl2/alcohol solvents. Also it was
found that the interaction of [MnTPP(OAc)] and manganese(III) tetramesityl porphyrin acetate
[MnTMP(OAc)] with n-Bu4NIO4 in the presence of Im but in the absence of alkenes yields
[MnTPP(O)(Im)]+ and [MnTMP(O)(Im)]+ complexes. The formation of the Mn=O species for the
small linear alcohols was faster than for the larger ones, whereas the stability of the Mn=O complex
was greater in the presence of the bulkier alcohols.
Keywords: Solvent
Epoxidation.
Effects,
Manganese
porphyrins,
Periodate,
Mn=O
species,
Catalytic
O-2
Tetranuclear CuII complexes with double µ-phenoxo and µ1,1-azido bridges and Schiffbase ligand
Aliakbar Dehno Khalaji
Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran
(e-mail: [email protected] & [email protected])
Research based on new Schiff bases and their metal complexes represents one of the most active
areas of material science, catalysis and chemical research. Tetradentate Schiff bases with N2O2
donor set atoms provide suitable coordination environments for a wide variety of metal ions and
can readily form binuclear and halogen carrying complexes with copper (II) ions. Synthesis of new
tetranuclear complexes have been importance for their interesting magnetic properties and as
model compounds for the metalloproteins and as precursors for high nuclearity cluster synthesis.
Herein, by slightly changing the synthetic conditions, two closely related linear tetranuclear CuII
complexes with the symmetrical tetradentate Schiff base ligand Mesalpn and with azide ions have
been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy, CV, EPR
spectra and variable temperature magnetic measurements. Single crystal X-ray diffraction studies of
the green [Cu4(µ-Mesalpn)2(µ1,1-N3)2(N3)2] and the red [Cu4(µ-Mesalpn)2(µ1,1-N3)2(N3)2(H2O)2]
crystals shows that the coordination environment of the two µ-phenoxo and µ1,1-azido bridged
isomorphous tetranuclear CuII complexes are slightly different. Thus, both complexes are formed by
very similar building units, although with a significant variation in the bridging Cu-O(phenoxo)-Cu
and Cu-N(azido)-Cu bond angles.
Keywords: Tetradentate; Schiff-bese; Crystal structure; Copper(II); Tetranuclear
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O-3
Synthesis, Characterization and Crystal structures of a New Proton Transfer Compound
of Acridine with Pyridine-2,6-dicarboxylic Acid and of the Palladium(II) Complex with
Coordination of Acridine
Zohreh Derikvand *,a, Marilyn M. Olmstead b
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Khorramabad Branch,
Khorramabad, Iran,
b
Department of Chemistry, One Shields Avenue, University of California, Davis, CA 95616-5292,
USA,
([email protected])
a
A new proton transfer ion pair of acridine with pyridine-2,6-dicarboxylic acid, and the neutral
complex resulting from its reaction with palladium(II) were synthesized and characterized by
elemental analysis, 1H NMR, IR spectroscopy and single crystal X-ray diffraction method. The
chemical formulas for the proton transfer ion pair 1 and complex 2 are (acrH)+(pydcH)−. H2O, and
[Pd(pydc)(acr)], respectively, where pydcH2 = pyridine-2,6-dicarboxylic acid and acr = acridine. A
number of intermolecular O–H···O, O–H···N and N–H···O hydrogen bonding interactions, as well as
π–π stacking, play important roles in the structure of compound 1. An unusually strong N–H···O
hydrogen bond connects (acrH)+ and (pydcH)−. In compound 2, acridine and (pydc)2– are
coordinated to palladium(II) as mono- and tridentate ligands, respectively. The structure features
extensive π–π interactions between the acridine rings as well as pairwise stacking of the complexes
via π–π stacking of the pydc rings.
Keywords: Proton transfer, Ion pair, Crystal structure, Pyridine-2,6-dicarboxylic acid, Acridine,
Palladium(II) complex.
O-4
Potentiometeric determination of some inorganic ions in aqueous solutions using
polypyrrole indicator electrode
a, b
F. Emsakpoura, R. Ansari b,*
Department of Chemistry, University of Guilan, Rasht, Iran
(e-mail: [email protected])
This paper describes a potentiometric titration for determination of halides at low concentrations.
The suggested microelectrode is based on a polypyrrole chloride thin layer deposited on a pencil
graphite microelectrode (PGE/PPyCl). A two-electrode system comprised of either a pencil graphite
working electrode (0.5mm diameter), silver counter electrode was used for electropolymerisation.
The monomer solution (pyrrole) was prepared using 0.10M pyrrole in NaCl 0.2M in distilled water.
Electrodeposition was performed galvanostatically (Id=2 mA/cm2) for 20 minutes. The pencil
electrode coated or modified by PPy/Cl polymer was then used as indicator electrode for
determination of end-point in potentiometric titration of halide ions. It was found that the proposed
PGE/PPyCl indicator electrode enables low concentrations of halide (ppm) to be determined using
potentiometric titration which is not actually possible with the silver electrode.
Keywords: potentiometric titration, halide ions, indicator electrode, polypyrrole, pencil graphite.
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O-5
Synthesis and characterization of [Co{(naph)2dien}(amine)]BPh4 and
[Co{(naph)2dpt}(amine)]BPh4 compelexes. Investigation of steric effects on their
redox and spectral properties
a
Farzaneh Fadaeea, Mehdi Amirnasra*, Kurt Mereiterb
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
b
Faculty of Chemistry, Vienna University of Technology, Getreidemarkt, Vienna, Austria
Two series of complexes of the type [CoIII{(naph)2dien}(amine)]BPh4 {(naph)2dien = bis-(2hydroxy-1-naphthaldimine)-N-diethylenetriamine dianion, and amine = piperidine (pprdn) (1),
pyrrolidine (prldn) (2), pyridine (py) (3), N-Methylimidazole (N-MeIm) (4)}, and
[CoIII{(naph)2dpt}(amine)]BPh4
{(naph)2dpt
=
bis-(2-hydroxy-1-naphthaldimine)-Ndipropylenetriamine dianion, and amine = piperidine (pprdn) (5), 3-Methylpyridine (3-Mepy)
(6)}have been synthesized and characterized by elemental analyses, IR, UV–Vis, and 1H-NMR
spectroscopy. The crystal structure of 2 and 6 has been determined by X-ray diffraction. The
electrochemical behavior of these complexes, with the goal of evaluating the effect of axial and
equatorial ligation on the redox properties, is also reported. The redox potentials of the central
cobalt ion show a relatively good correlation with the σ-donor ability of the axial ligands. The
influence of the pentadentate ligand as well as the effect of the ancillary ligand has also been
studied using spectral and electrochemical data. This study shows that the spectroscopic and
electrochemical properties of these complexes are controlled by the structural requirements of the
pentadentate ligand.
Keywords: Cobalt (III) complexes; Pentadentate Schiff base ligand; cyclic voltammetry; X-ray
crystal structure.
O-6
Chemical Role of Alkali Ion by Catalytic Performance Studies over
(4%Mn+0.78%A+3.13%W)/SiO2 Catalysts for Oxidative Coupling of Methane
Reaction
Z. Gholipoura , A. Malekzadeh*a , A. Khodadadib , Y. Mortazavib
a
: School of Chemistry, Damghan University (DU), Damghan, I. R. Iran.
b
: Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering,
University of Tehran, Tehran, I. R. Iran.
[email protected]
Oxidative coupling of methane reaction was studied over [4%Mn+0.78%A+3.13%W]/SiO2 catalysts
under fixed bed condition with CH4/air = 1 or CH4/O2 = 5, feed flow rate of 112 mL/min (STP) and
GHSV = 13200 mL/gCat⋅h. Here A is an alkali ion of Li, Na, K or Cs. The chemical role of alkali ion is
researched as the main goal. Prepared catalysts were characterized by the FTIR, XRD, TPR and
SEM analysis. Different metal–metal interactions comprising transition metals and alkali ions are
important for proper performance of a catalyst. Crystallization of catalysts that takes place during
the preparation of catalysts and completes under the OCM reaction is evidence for a structural
flexibility of catalysts under the reaction conditions. Crystalline structure of catalysts, a requirement
for the formation of a selective OCM catalyst, depends on the alkali ion, is observed to be quartz
and cristobalite in case of Li and the other alkali ions, respectively and promoted under the OCM
reaction conditions. The oxy–anion acceptance capacity of Na2WO4/SiO2 in catalyst containing
different metal oxides, however, is the other important parameter, affecting the catalyst activity and
selectivity.
Keywords: Oxidative coupling of methane (OCM), quartz, cristobalite , Alkali ion, TPR.
6
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O-7
Synthesis and Characterization of Dinuclear Copper(ІІ) complexes with Imine-Oxime
groups
H. Ghorbanpour, H. Golchoubian*
Department of Physical-Inorganic chemistry, University of Mazandaran, Babolsar, Iran
(e-mail:[email protected])
Many dinuclear complexes of Copper(ІІ) in which two copper atoms are linked by two mono- or
polyatomic bridges are known. Recently dinuclear complexes with hydroxo and tetraketonate
bridges were prepared in our lab. These types of complexes demonstrated distinctive
solvatochromic properties. Thus we motivated to prepare dinuclear copper(II) complexes containing
Imine-Oximes ligands that their oxygen atoms operate as bridges . In this regard a series of
dinuclear complexes illustrated below with different R groups (R = Me, Et and Iso-pro) were
prepared. To prepare these complexes, the tridentate ligand was synthesized, first with
condensation of an equimolar of N,N-dialkylethylendiamine with Diacetylmonoxime. Then the ligand
which is abbreviated as dox-enR2 was reacted with copper(II) perchlorate to generate desired
complexes, [Cu2(dox-enR2)2](ClO4)2. The complexes were characterized by elemental analysis,
molar conductance, IR and UV-Vis spectroscopies. The complexes are soluble in various solvents
and show solvatochromic properties. The solvatochromism studies of the complexes demonstrated
that with increasing the stric hindrance around the copper(II) ion the complex becomes more
solvatochromism , that means, showing grater ∆λ value with change in solvents .
Keywords: Dinuclear copper(ІІ), Imine-oxime, Diacetylmonoxime, Solvatochromism studies.
O-8
Assembly of Cyclometalated Organoplatinum Complexes through a Bridging
Diphosphine Ligand
Mohsen Golbon Haghighi*, S. Masoud Nabavizadeh, Mehdi Rashidi
Chemistry Department, College of Science, Shiraz University, Shiraz 71454, Iran
Email: [email protected]
The chemistry of cyclometalated organometallic compounds is of great current interest, based on
applications of such compounds in stoichiometric or catalytic organic synthesis and in sensing and
functional materials.
In this regard, it has been shown that the chelate ring in complex can be opened by reaction with a
chelating diphosphine, dppe = bis(diphenylphosphino)ethane, to give the monodentate 2pyridylphenylplatinum complex. With only a half equivalent of the diphosphine, the symmetrical
bridged binuclear complex was formed. In this study, several new cyclometalated diorganoplatinum
complexes containing dppe ligand are synthesized. Thus, the binuclear symmetrical binuclear
complex was synthesized using the appropriate monomeric precursor [Pt(CN)SMe2(R)] in which CN
= deprotonated 2-phenylpyridine (ppy), deprotonated Benzo[h]quinoline (bhq); R = methyl (Me),
para-tolyl (p-T), as shown in the scheme. The complexes were fully characterized by multinuclear
(1H, 31P, and 195Pt) NMR spectroscopy and X-ray crystallographically, and it is shown that some of
the bhq complexes undergo supramolecular self-assembly through π-stacking.
Keywords: Organometallic, Cyclometalated Compound, Diorganoplatinum, Supramolecular, Selfassembly.
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O-9
A Computational Study on Some Aspects of the ROP Mechanism of Polyphosphazenes
(1)
B. Golzadeha,b,*, A. Akbaria, H. Ghatezadeha, Y. Ebrahimipoura, M. Ahmadia
a
Department of Chemistry, Payame Noor University (PNU), Mashad, Iran
b
Department of Chemistry, Payame Noor University (PNU) , Amol, Iran
Polyphosphazenes comprise by far the largest class of inorganic macromolecules and their general
molecular structure is (-N=PR2-). A major route to phosphazene polymers involves the ring-opening
polymerization (ROP) of the cyclic trimer [PCl2N]3 to the polymer [PCl2N]n. The nitrogen atoms of
[PCl2N]3 is known to be a weak base and experimentally the reactions of [PCl2N]3 with various Lewis
acids, reportedly gave complexes of various stoichiometries. In this study, which was done with the
ADF2009 package, the geometrical parameters of the [PCl2N]3[MCl3]n adducts where M= B, Al, Ga,
In, Tl and n=1, 2 with the LDA, GGA-BLYP and Hybrid-B3LYP methods of density functional theory
(DFT) using two combination basis sets of Slater-type orbitals (DZ, DZP) have been studied.
Results showed that the phosphazene rings in the [PCl2N]3MCl3 adducts are somewhat distorted
from planarity to give chairlike structures in which the nitrogen atom bound to the group 13
element and the opposite phosphorus atom are below and above the plane of the remaining ring
atoms. The ability to undergo ROP, is also studied by calculating various parameters for three
cations [P3Cl5N3X]+ where X=H, CH3, Si(CH3)3 and Si(C2H5)3. Results were compatible with
experimental experiences reported in previous articles.
Keywords: Polyphosphazenes, ROP, Geometrical Parameters, DFT
O-10
Kinetic β-Deuterium Isotope Effect in the Reaction of Diimine-dimethylplatinum(II)
Complexes with Ethyl Iodide
a
S. Habibzadeha,*, S. M. Nabavizadeha and M. Rashidia
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, 71454, Iran
β-Hydride elimination of σ-bound alkyl ligands and its reverse process of olefin insertion into M-H
bond, are fundamental in organometallic catalysis. Formation of a β-hydrogen interaction stabilizes
the intermediates in these processes and increases the rate of the related reactions. The concept of
hyperconjugative stabilization of radicals or cations has been used to explain the β isotope effects in
processes involving radical or carbonium ion formation in the transition state. In this work, kinetic
β-deuterium isotope effects have been determined for the reactions of diimine-dimethylplatinum(II)
complexes [PtMe2(NN)] (NN = bipyridine (bpy) or 4,4'-bis(tert-butyl)-2,2'-bipyridine (tBu2bpy)) with
C2H5I/C2D5I, in acetone or benzene solvent, at different temperatures. These reactions, that are
known to take place by classical SN2-type mechanism, have indicated significant positive kinetic βdeuterium isotope effects, (kH/kD)β, values of up to 2.41. The effect is significantly solvent and
temperature dependent, but is independent of the nature of NN. The secondary kinetic α-deuterium
isotope effects, (kH/kD)α, in the reaction of CH3I/CD3I with the same complexes were also studied
(by 1:1 molar ratio technique) in order to confirm that (kH/kD)α values would be close to 1 and
therefore has not contributed to the obtained (kH/kD)β. The observation of high positive (kH/kD)β
support the formation of β-hydrogen agostic interaction during the reaction progress.
Keywords: Kinetic, β-Isotope effect, Platinum, Agostic interaction
8
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O-11
Photooxygenation of alkenes by molecular oxygen in the presence of porphyrins and
chlorin sensitizers under visible light irradiation
M. Hajimohammadi and N. Safari*
Chemistry Department, Shahid Beheshti University, G.C, Evin, Tehran, 19839-63113, Iran
(email: [email protected])
Metalloporphyrins have been found to be efficient biomimetic catalysts for hdrocarbon oxidation by
using molecular oxygen and various oxygen transfer reagents. However, finding a catalytic system
for hydrocarbon oxidation by O2 under mild conditions is still a challenging issue in the laboratory
and industry. Photooxidation of alkenes by molecular oxygen and visible light in the presence of
tetraphenylporphyrin (H2TPP), tetramesityleporphyrin (H2TMP), tetrakis pentaflourophenylporphyrin
(H2TPFPP) and tetrakis(2, 3 dimetoxyphenyl)porphyrin T(2, 3-OMeP)P and metalloporphyrins such
as ClFeTPP, ClMnTMP, ClMnTPP, ClMnTPFPP, ClCoTPP and ZnTPP has been performed.
Photooxidation of alkenes with tetraphenylchlorin (H2TPC) as the sensitizer with visible light has
also been studied. The conversion rates for alkene oxidation were in the order of free base
porphyrins > chlorin > metalloporphyrins. In the Presence of NaN3/ Na2SO3 the yeild of oxidation
products and conversion percentage is considerably reduced, confiring involvement of 1O2 in the
mechanism.
Keywords: Photooxygenation, Porphyrin, Chlorin, Singlet oxygen, Visible light.
O-12
Preparation and Characterization of Surface Modified Metal Oxide Nanoparticles
a
Mayram Adineha, Mostafa M. Aminia*
Department of Chemistry, Shahid Beheshti University, G.C. ,Tehran, Iran
The nanosize metal oxides are subject of greet interest due to their potential applications in various
fields including electronic and magnetic industry. Among many metal oxides, iron, copper and nickel
oxide are most often used in industry and for improvement of their behavior and also expend of
their application, modification of oxides surface with various functional group is necessary. In this
work the surface of several metal oxides (magnetic and non magnetic) were modified with various
silanation agents in one-step process. Iron, copper and nickel oxides were synthesized in
nanometer
scale
and
then
their
surface
were
modified
with
N-[3(triethoxysilyl)propyl]isonicotinamide, trithoxysilylpropylamine and trithoxysilylbutironitrile. The bare
metal oxides and their surface modified materials were characterized by infrared spectroscopy and
X-ray powder diffraction. In addition, metal oxides surface functional group loading was determined
by elemental analysis. The surface modified metal oxide have been used to remove various metal
ions including lead from various matrixes specially contaminated water and simulated plasma.
Results showed that the pyridine functionalized metal oxides are effective materials for removing
metal contaminant from water and plasma in comparison with amine and nitrile functionalized metal
oxides.
Keywords: Metal oxide, Surface modification, Heavy metal remove, contaminated water, simulated
plasma
IICC12
9
O-13
Processing Parameters on the Stabilization of Ammonium Azide Particles by Using Taguchi
Orthogonal Array Design Method
S. G. Hosseini, A. Eslami*
Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-1467, Babolsar, Iran
This work is devoted to reduce spontaneous sublimation of ammonium azide by mean of
microencapsulation technique. In the present study, influence of various processing parameters on
the mircoencapsulation of NH4N3 particle with nitrocelloluse through a solvent/non-solvent
procedure which is based on the coacervation principle has been studied. Taguchi L-9 orthogonal
array design is used for analyzing the effect of percent of stabilizer, addition time of non-solvent,
volume of non-solvent and stirring speed of the mixture on the coating properties. The individual
effect of each parameter on the coating properties in correlation with surface morphology and
thermal stability of NH4N3 particle is discussed. It is found that Taguchi design is adequate to
understand the effect of processing parameter in the limited number of experiments. Also, the
kinetic parameters such as activation energy and frequency factor of the sublimation processes of
pure and microencapsulated NH4N3 at optimum condition were obtained from the DSC data by nonisothermal methods proposed by ASTM E696. Our findings showed that treated NH4N3 has much
lower sublimation rate as compared to the pure one and maximum sublimation temperature of
most stabilized coated NH4N3 is about 70 ºC higher than that of pure one.
Key words: NH4N3, sublimation, Microencapsulation, Thermal stability, Statistical optimization.
O-14
Nickel(II), Copper(II), and Cobalt(II) Complexes with a Hydroxyl Pendant-Armed
Macrocyclic Ligand: Synthesis, Characterization, and Crystal Structures
S. A. Hosseini-Yazdi*, A. A. Khandar, M. Alizade
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Iran
The interaction of metal ions with oxygen-nitrogen donor macrocycles has been the subject of a
range of studies. A number of these investigations have involved synthetic, kinetic, thermodynamic,
and structural aspects of complex formation with a range of metal ions. The reactions of different
nickel(II), copper(II) and cobalt(II) salts with a mixed-donor macrocyclic ligand L
(6,7,8,9,10,11,18,19-octahydro-5H, 17H-dibenzo[f,o] dioxadiazacyclohexadecin-18-ol), potentially
pentadentate N2O3 donor sets containing one pendant alcohol function have been investigated.
The physical properties and the chemical structures MLCl2 (M = Ni2+, Cu2+, Co2+) complexes
have been characterized by using IR, UV-Vis spectroscopy and conductance measurements. The Xray determination has been employed to probe the nature of the respective complexes in solid
state. In [NiLCl2] complex the pendant hydroxyl arm of macrocycle remains uncoordinated and
ligand acts as tetradentate N2O2 donor atoms. The coordination sphere is completed by two chloride
anions and nickel atom is six-coordinate with a distorted octahedral geometry. Structure of CuLCl2
reveals the presence of two Cu-macrocycle complex molecules forming a centrosymmetric dimmer.
The pair of chloride Cl ions belonging to both halves of the dimmer play a role of the bridging
ligands. Each Cu1 ion has a deformed square pyramidal coordination sphere with two chloride ions
and two macrocycle N atoms liganded in the equatorial positions. When L reacts with CoCl2 the
product is a novel structure of a coordination polymer.
Keywords: Copper; Cobalt; Nickel; Macrocyclic Ligands; Coordination Polymer
10
IICC12
O-15
Prototropic and Cobaltotropic shifts on Indenyl rings. A Theoretical Study
Z. javanshira,c*, S. Jameh-Bozorghib, M. Davishpoorc and H. R. khalilic
Department of Chemistry, Faculty of Science, young Reaserchers club, Islamic Azad Universit,
Ardabil Branch, Ardabil, Iran
[email protected]
b
Department of Chemistry, Graduate Faculty, Toyserkan branch, Islamic Azad University,
Toyserkan, Iran,
c
Department of Chemistry, Faculty of Science, Islamic Azad University, Arak Branch, Arak, Iran
a
Energetic and structural behaviour of, migrations of proton and the tricarbonylcobalt group on the
1-Indenyl(tricarbonyl)cobalt ring were investigate using Density functional (B3LYP) methods . The
energy barrier of Prototropic shift is higher than cobaltotropic shifts. Consequently, the rate of
sigmatropic migration of hydrogen atom is much slower than cobalt atom migration. This results
indicate that the most stable isomers of compounds 1–4 are the allylic isomers (the Co(CO)3
fragment in an allylic position or compound 1). This behaviour is in good agreement with
experimental data.
Keywords: prototropic shift, cobaltotropic shift, DFT, B3LYP
O-16
Synthesis of New phosphonium Ylides Containing Thiophene and Furan Rings and Study
of Their Reaction with Mercury(II) Halides: Spectral and Structural Characterization
Seyyed Javad Sabounchei * a, Vida Jodaian* b, Sadegh Salehzadeh a,
Sepideh Samiee a, Alireza Dadrass a, Mehdi Baya a t and Hamid Reza Khavasi C
a
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 65174, Iran
Department of chemistry, Islamic Azad University, Islamshahr Branch-33135/ 369, Tehran, Iran
C
Department of chemistry, Shahid Beheshti University, Evin, Tehran, 19839-63113, Iran
e-mail: [email protected] & [email protected]
Abstracts: Reactions of phosphonium ylides (4-MeC6H4)3PCHCO(2-C4H3S)(TPTPY), Ph3PCHCO(2C4H3O)(FPPY), and (4-MeC6H4)3PCHCO(4-BrC6H4)(BBTPPY) with HgX2 (X=Cl, Br and I) in equimolar
ratios in MeOH as solvent leads to the binuclear products. The bridge splitting reaction of the
binuclear complex [{HgI2(BBTPPY)}2] by DMSO yields the mononuclear complex [HgI2.
(BBTPPY)(DMSO) ]. This bridge-splitting reaction can also be a method for the synthesis of
mononuclear products. C-Coordination of the ylide and O-coordination of DMSO are demonstrated
by a single-crystal X-ray analysis of the mononuclear complex. Characterization of the obtained
compounds was also performed by means of elemental analysis and IR and 1H-, 31P- and 13C-NMR
spectroscopy. A theoretical study of some HgII complexes with phosphonium ylides is also reported.
Keywords: mononuclear complex, binuclear complex, phosphonium ylides, bridge splitting
IICC12
11
O-17
Synthesis and characterization of molybdenum complex with bidentate Schiff base
ligand supported on magnetic nanoparticles
Zeinab Kashef, Majid Masteri-Farahani *
a Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
(e.mail:[email protected])
Modified magnetic materials are nowadays well-known and have been investigated intensively due
to their potential applications in many areas, such as biology, medicine and the environment.
Another important example is removal of toxic elements from industrial wastes. These materials are
composed of an iron oxide core containing nanometer sized particles and presents super
paramagnetic behavior. Functional groups tailored for specific tasks are anchored as an organic
molecule shell around of the core. These particles are capable of forming stable aqueous
suspensions and may be easily redispersed after agglomeration in the presence of a magnetic field.
We report here the synthesis of silica coated magnetic nanoparticles modified with 3aminopropyltrimethoxysilane.Reaction of this material with salicylaldehyde afforded the
corresponding
supported
Schiff
base
ligand.
Subsequent
reaction
with
bis(acethylacetonato)dioxomolybdenum(IV) leads to molybdenum complex supported on silica
coated magnetic nanoparticles. Characterization of these materials was carried out with FT-IR,
powder X-ray diffraction (XRD) and vibrating sample magnetometry (VSM).The resultant materials
successfully catalyzed the epoxidation of cyclooctene, cyclohexene and 1-hexene with tert-butyl
hydroperoxide to the corresponding epoxides with 98-100% selectivities. A new heterogeneous
epoxidation catalyst was prepared with immobilization of a molybdenum complex on the surface of
nanomagnetite material.
keywords: Molybdenum, Magnetic Nanoparticles, Epoxidation, Supported Ligand
O-18
Surprises in the Study of Ruthenium-catalyzed Stereo- and Chemoselective ldolizations
E. Keshavarz, K. Tabatabaeian*, M. Mamaghani and N. O. Mahmoodi
a
Among the transition metal Lewis acids, ruthenium salts and complexes display remarkable
properties. Ruthenium is known to catalyze a variety of organic transformations. In this report, we
shall focus on some of our recent studies where we employ ruthenium compounds as an efficient
catalyst for aldol reactions. Recently, we have examined an efficient protocol for the cross aldol
reaction in the presence of RuCl3.nH2O/PPh3. In this protocol, the reaction of 1-(thiophen-2yl)ethanone with aldehydes resulted aldol adducts in good yields without the formation of any side
product. The study of the RuIII/PPh3-promoted aldol reaction urged us to investigate the aldolization
of aryl alkyl ketones with aromatic and heteroaromatic aldehydes in the presence of RuCl2(PPh3)3.
RuII catalyzed cross aldol reaction proceeded at 80 °C, furnishing a wide variety of β-hydroxy
ketones with moderate diastereoselectivities and in good yields. This led us to discover unexpected
effects of the nature of chiral ligand on the RuIII-catalyzed aldolization of aromatic aldehydes with
ketones. In this method, the aldol reaction proceeded smoothly, affording the corresponding
product in good yields and complete diastereoselectivities, favoring the syn diastereomer. The
presentation of this protocol will be the last commented reaction of this report.
Keywords: RuCl3.nH2O, PPh3, RuCl2(PPh3)3, BINAP, Aldol reaction.
12
IICC12
O-19
Adsorption studies of Sm(III) from water by Sm(III) Imprinted complex on Alumina
surface
Nasrin Khaledian* Mahboobeh Manoochehri Homayoon Ahmadpanahi
Department of Chemistry, Islamic Azad University, Central Tehran Branch, Tehran - Iran
Molecular imprinting is a technique for preparing polymeric materials that are capable of
recognizing and binding the desired molecular target with a high affinity and selectivity. Molecularly
imprinted polymers (MIPs) are synthetic polymeric materials with specific recognition sites
complementary in shape, size and functional groups to the template molecule, involving an
interaction mechanism based on molecular recognition. In recent years, molecular imprinting has
attracted considerable interest in many areas of chemistry, biochemistry, and biotechnology.
Selectivity is the predominant advantage of MIPs in separating and analyzing complicated samples,
such as environmental and biological samples. It is known that heavy metal ion contamination
represents a significant threat to the ecosystem and especially to people due to the severe
toxicological effects on living organisms.samarium is one of these heavy metals.In this study a new
Sm(III)-imprinted mercapto-functionalized Alumina sorbent was synthesized by easy reaction by
combining a surface imprinting technique for selective solid-phase extraction of trace Sm(III) prior
to its determination by Inductivly Coupled Plasma optical emission spectroscopy(ICP_OES). The
Sm(III)-imprinted sorbent was characterized by IR spectroscopy and element analysis. Compared to
non-imprinted polymer particles, the ion-imprinted polymers had higher selectivity And adsorption
For Sm(III). The method was successfully applied to the analysis of trace Sm(III) in water sample
solutions while the influence of various factors such as PH and initial concentration were studid.The
equilibrium sorption isotherms also were studied using Freundlich Langmuir and Temkin isotherm
models.
Keywords: Molecularly imprinted polymers; Sm(III)-imprinted mercapto-functionalized Alumina
sorbent;Adsorption; solid-phase extraction
O-20
Photocatalytic activity of ZnO and CdS nano particles for degradation of aromatic-based
azo-azomethine
F.khodam, H. Khanmohammadi*
Chemistry department, Arak University, Arak, Iran, P. O. Box 38156
E-mail:[email protected]
Pollution of water by organic azo dyes is a serious problem in recent years. The removal of azodyes from wastewater is an important challenge for dye industries because the synthetic azo-dyes
are stable and difficult destroy by common treatments. One of the prominent extent methods for
degradation of azo-dyes is application of nano particles as photodegradation catalyst. Hetrogeneous
photocatalysis employing nano–sized metal oxids and or metal sulfide has been an attractive
research and development subject in water treatment owing to its proven capability in the
degradation of aromatic azo dyes. In the present work a new azo-azomethine aromatic based dye
(H2L) was synthesized by condensation reaction of 13-bis((aminoethyl)thio)benzene with azocoupled 1-(3-formyl-4-hydroxy phenyl azo)-4chlorobenzen. The photocatalytic activity of ZnO and
CdS nano particles for degradation of the prepared dye in the presence or in the absence of UV
irradiation has been studied. A series of tests were carried out to define the best condition for
degradation of the azo-azo methane dye (H2L). The result showed that the prepared dye was
decolorized effectively in the presence of nano ZnO+H2O2 under UV irradiation.
Keywords: azo-azo methane, decolorized, photodegradation
IICC12
13
O-22
Iron(II)-superoxo complex can effect aliphatic C–H bond hydroxylation reactions but
not aromatic hydroxylation reactions
b
Reza Latifi, a,b Laleh Tahsini,b,c Wonwoo Nam, *c and Sam P. de Visser *b
a
Chemistry Department, Shahid Beheshti University, Evin, Tehran, Iran.
Manchester Interdisciplinary Biocentre and School of Chemical Engineering and Analytical Science,
University of Manchester, 131 Princess Street, Manchester, M1 7DN United Kingdom.
c
Department of Chemistry and Nano Science and Department of Bioinspired Science, Ewha
Womans University, Seoul 120–750, Korea.
In recent years it has been shown that metal-peroxo and/or metal-superoxo intermediates can
occasionally act as oxidants of, e.g., C–H abstraction reactions. Thus, in the enzyme isopenicillin N
synthase, an iron(III)-peroxo intermediate initiates the first of four consecutive hydrogen atom
abstraction reactions from the substrate that eventually leads to two ring-closure processes. To
understand the mechanism and substrate range of catalytic oxidations by iron(III)-peroxo and its
isoelectronic iron(II)-superoxo complex we have performed a density functional theory (DFT) study
on the aliphatic and aromatic hydroxylation of a nonheme iron(II)-superoxo complex and compare
its activity with its corresponding iron(IV)-oxo complex. density functional theory calculations on
(14TMC)FeIIOO•– show the first example of a nonheme superoxo complex that it is able to activate
C–H bonds of aliphatic substrates, although only relatively weak C–H bonds will be activated by this
oxidant. A comparison with the energetics and mechanism of iron(IV)-oxo porphyrin oxidants shows
that these are superior to the (14TMC)FeIIOO•– complex with respect to aliphatic and aromatic
hydroxylation reactions.
Keywords: C–H abstraction, iron(II)-superoxo, (14TMC)FeIIOO•–, DFT
O-23
Synthesis and Study on Coordination Chemistry of Fullerene-bonded Macrocyclic
ligands With Various Ring Size Azacrown
M. Alishah Aratboni, B. Ghanbari*
Department of Chemisty, Sharif University of Technology, Tehran, Iran
[email protected]
The new form of carbon, namely [60]fullerene, has generated an avalanche of research activities. It
has been shown that [60]fullerene can a great electron affinity (2.69 eV). On the other hand, host
molecules for inclusion of fullerenes are of great importance because of their practical application to
extraction and chemical modification of fullerenes. Thus, the design and synthesis of host molecules
with reverse selectivity is of practical interest. For instance, γ-cyclodextrin, calixarenes were able to
extract C60 from a mixture of C60 and C70. In the context studies, the [60]fullerene complexation
with 14-,15-,16-,17-,membered cis-N2O2 macrocycles were studied by UV-visible spectroscopy. The
formation constants arising from the complexation of [60]fullerene with these azacrown
macrocycles, having various ring size, were determined in CH2Cl2 medium applying BenesiHildebrand equation. The stoichiometry has been found by the Job method in each case. The
thermodynamic parameters, e.g. enthalpies (∆H) and entropies (∆S) for the complex formations
were also calculated. Experimentally, it was found that as the macroring size of the azacrown
increases the [60]fullerene complexation were favored in terms of their Kassociation (Figure2). The 1H
NMR (500 MHz probe) spectra of these complexes in their CDCl3 solutions were also confirmed on
these interactions. The differences in the chemical shift for the macroring backbone (in Hz) showed
that the amine functional groups could be the more eligible candidate as donor atoms in
complexations.
Keywords: Fullerene, Macrocycle, Azacrown, Complexation
14
IICC12
O-24
The study of unfamiliarity alkyl shift: Some new homo- and heterobimetallic complexes
with dicompartmental macroacyclic ligand containing dangle arms
H. R. Mardani, H. Golchoubian *
Department of Chemistry, University of Mazandaran, Babolsar, Iran
The study of bimetallic complexes is of current interest in unique physicochemical properties and
functions associated with metal–metal interaction or cooperative effect of a pair of dissimilar metal
ions. So far, many efforts have been developed to the design of compartmental ligands possessing
two dissimilar metal bonding sites with respect to the nature of donor atoms, the cavity size and
the steric requirement for coordination of metal ions. In this work, we design new dicompartmental
ligands that containing two different sites: one is N4O2 (closed-site) and another is N2O2 (open-site)
that the link at open-site is disconnected. We are interested in studying the influence of ligand
modification on the geometry of the metals in both coordination sites of this macroacyclic ligand
and also investigating the controlling factor on the methyl or alkyl shift. The prepared complexes
were characterized by elemental analysis, spectroscopies techniques, molar conductance
measurements and X-ray crystallography.
Keywords: Dicompartmental ligand, Homobimetallic complex, Heterodinuclear complex, Alkyl shift
rearrangement
O-25
Synthesis and spectral investigation of tin complexes containing tridentate NNO-donor
Schiff base ligands
M. Moalemian a,*, A.H. Kianfar b and M. Hadiana
aDepartment of Chemistry, Islamic Azad University, Gachsaran Branch, E-mail:
[email protected] & [email protected]
bDepartment of Chemistry, Yasouj University, Yasouj, E-mail: [email protected]
we reported here preparation and characterization of the new tin complexes. The Schiff bases
ligands were prepared from the condensation of Salicylaldehyede or 5-Bromo Salicylaldehyede with
4-Nitro-1,2-Phenyldiamine in ethyl alcohol as a solvent. The separated precipitate was filtered,
washed several times with minimum amount of ethyl alcohol and dried under vacuum at room
temperature. Tin complexes under investigation were synthesized as follows; the ligand was
dissolved in (20 mm) ethanol and added to a metal salt(Bu2SnO) ethanolic solution (20 mm). The
reaction molar ratio is (1:1). The mixture was refluxed for 5h; the volume of the mixture was
reduced to one-third. On cooling a crude product was formed, which is collected by filtration and
washed several times with ethanol and dried over anhydrous CaCl2. The solid products are well
characterized through its elemental analysis, melting points and electronic spectra, along with the
assignment of their infrared spectra for most of the fundamental vibrations. Infrared spectroscopy
has been widely used as a powerful means of distinguishing between the three possible donation
sites of Schiff bases. A strong band at 1633 cm−1 is assigned to the ν(C=N) vibration. The broad
band of medium intensity that appear in the range 3500-3400 cm−1 is due to the O−H stretching
vibration of the phenolic OH group. A considerable lowering of the ν(C=N) frequency is observed in
the spectra of the two complexes, indicating a decrease in the stretching force constant of the C=N
bond as a consequence of the coordination of the nitrogen atom to the metal ion. The bands at
1425 cm−1 and 1314 cm−1 are due respectively to ν(N=O) and νas(NO2).
Keywords:Tin complexes; Salicylaldehyede; 5-Bromo Salicylaldehyede; 4-Nitro-1,2-Phenyldiamine.
IICC12
15
O-26
Syntheses, characterization and solvatochromism studies of new mixed-chelate copper
(II) complexes
G. Moayyedi, H. Golchoubian*
Department of Physical-Inorganic chemistry, the university of Mazandaran, Babolsar, Iran
(e-mail : [email protected])
Mixed copper (II) complexes with the general formula [Cu(Cl-acac)(diamine)]X where Cl-acac = 3chloroacetylacetonate ion, diamine = N,N'-dimethyl,N'-benzyl-1,2-diaminoethane and X = BPh4-,
PF6-, BF4- have been prepared. The complexes were characterized on the bases of elemental
analysis, molar conductance, and UV-Vis and IR spectroscopies. The x-ray crystal structure of the
complex [Cu (Cl-acac)(diamine)](PF6-) (H2O) illustrated the expected structure as shown below. The
solvatochromic behaviors of the complexes were studied by UV-Vis spectroscopy. All complexes
demonstrated the negative solvatochromism. The results were feeded to SMLR (stepwise multiple
linear regression) computer program to determine the best model to interpret their
solvatochromism behavior. Although there are different solvatochromism parameters for solvents
the results showed the best model among them is the Donor Number of the solvent.
Keywords: Mixed-chelate, Solvatochromism, X-ray crystal structure, stepwise multiple linear
regression, diamine, Copper (II).
O-27
Synthesis, single-crystal structural determination and solution characterization of a
novel sandwich-type Manganese-containing Vanadotungstate
Mohammad Reza Mohammadia*, Mohammad Hakimia, Ulrich Kortzb and Bassil Bassemb
a
Chemistry Department, Payame Noor University (PNU), Mashhad, Iran
E-mail: [email protected]
b
School of Engineering and Science, Jacobs University, Bremen, Germany
The novel dimeric vanadotungstate, [V2W18Mn4(H2O)2O68]10-, has been synthesized by an unusual
reaction of Na12[Na2V2W18U2O72].38H2O with a solution of MnCl2. The reaction due to replace
uranyl groups and two Na with Mn atoms. The unambiguous characterization of
[V2W18Mn4(H2O)2O68]10- was accomplished by means of elemental analysis, IR, Raman, UV-Vis and
EPR spectroscopy, and confirmed by a single crystal X-ray structural analysis of the potassium salt.
The heteropolyanion consist of two lacunary A-[VW9O34]9- Keggin moieties linked via a rhomboid
Mn4O12 group leading to a sandwich-type structure.
Keywords: Crystal structures, Vanadotungstate, IR, EPR, sandwich-type
16
IICC12
O-28
Polymerization of Ethylene and Isobutylene catalyzed by β-Diketiminate Alkyl Al and Sc
Complexes: A DFT Study
a
Azadeh Moradzadeha,*, Alireza Ariafard b,a, Tahmineh Mehrabia
Deptartment of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Iran
b
School of Chemistry, University of Tasmania, Private Bag 75, Hobart, TAS, 7001, Australia
We theoretically studied the olefin polymerization catalyzed by β-diketiminate alkyl Al and Sc
complexes. The chain propagation step is a fundamental step in olefin polymerization and involves
the binding of olefin to the metal center followed by the olefin insertion into the metal-alkyl bond.
The propagation step of the terminal olefins follows two most common routes known as 1,2- and
2,1-insertion reactions. In the 1,2 insertion (region-regular), the unsubstituted olefin carbon binds
to the metal center whereas in the 2,1-insertion (region-error), the unsubstituted olefin carbon
binds to the α-carbon of the growing chain. Experimental and theoretical studies for early transition
metal systems demonstrated that the 1,2-insertion is the most accessible route. Our calculation for
the Al and Sc system also supports the more favorability of 1,2-insertion than 2,1-insertion.
According to the calculations, the alminum β-diketiminate catalysts prefer to interact with ethylene
and produces bicyclic complexes while the scandium β-diketiminate catalysts involve in the ethylene
polymerization reactions. It was also predicted that the reaction between the Al system and
isobutylene leads to the isobutylene polymerization while the use of Sc instead of Al decreases the
possibility of the polymerization process, because the propagation step on the Sc system is
calculated to be endothermic.
Keywords: Polymerization, bicyclic complexes, β-diketiminate, Aluminum, Scandium
O-29
The study of regioselectivity in the terminal alkyne (R’CCH) insertions into Pd-R donds,
where R = SiH3, SnH3, GeH3, SiMe3, Cl, SMe, SeMe, CH3 and R’ = NH2, CH3, CN
a
Alireza Ariafarda,b, Mahshid Moshtaghia*
Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University,
Shahrak Gharb, Tehran, Iran , Email: [email protected]
b
School of Chemistry, University of Tasmania, Private Bag 75, Hobart TAS 7001, Australia
In this contribution, we studied the 1,2- and 2,1-regioselectivity of terminal alkyne (R‫׳‬CCH)
insertions into Pd-R bonds, where R = SiH3, SnH3, GeH3, SiMe3, Cl, SMe, SeMe, CH3 and R ‫ =׳‬NH2,
CH3, CN. The migration insertion reactions in terminal acetylenes are a very important part in many
of the catalyzed processes by Pd or Pt. This reactions can be performed through either 1,2-insertion
or 2,1-insertion. In 1,2-insertion, the R group migrates to the internal carbon of the alkyne, while in
2,1-insertion, the R group migrates to the terminal carbon of the alkyne. We considered three
different R groups; 1) the π-donor groups such as Cl, SMe and SeMe; 2) the groups such as SiH3,
GeH3, SnH3 and SiMe3 that can expand their valence shell and thereby accept electron; and 3) the
groups that are neither π-donor nor electron acceptor. The π-donor groups preferentially undergo
1,2-insertion reactions. The groups that expand their valence shell, preferentially undergoes 2,1insertion reaction. The use of SiMe3 instead of SiH3 increases the electron density on the metal
center, lowering the energy barrier of the insertion reaction. The third category is the groups that
are neither π-donor nor electron acceptor such as CH3. Our calculations showed that these groups
are most likely to undergo the 2,1-insertion reactions better than the 1,2-insertion; although the
energy barrier difference between the 2,1- and 1,2-insertions is calculated to be very small.
Keywords: Regioselectivity, Insertion Reaction, Palladium, Density Functional Theory.
IICC12
17
O-30
Crystal structure and spectroscopic characterization of a dimeric [WOS3Cu3Cl(µ -bbd)]2
cluster
Seyed Ahmad Mousavi Fard and Azizolla Beheshti*
Department of Chemistry, Faculty of Sciences, Shahid Chamran University, Ahvaz, Iran
The reactions of [NH4]2[WOS3] with one equiv. of 1,1′-(1,4-butanediyl)bis(3,5-dimethyl-pyrazole)
(bbd) in DMF afforded a dimeric cluster [WOS3Cu3Cl(µ -bbd)]2 .The complex was characterized by
elemental analysis, IR, UV-vis, 1HNMR and single-crystal X-ray crystallography. An X-ray
crystallographic analysis reveal that [WOS3Cu3Cl(µ -bbd)]2 crystallizes in the monoclinic space group
P121/n1 with Z=2. The neutral cluster consists of two teranuclear nidoshaped WOS3Cu3
fragments, connected by a pair of µ –bbd bridges to form a unique centrosymmetric double nidoshaped structure. In the WOS3Cu3 core, the tungsten, three sulphure and three copper atoms are
arranged on seven of the vertices of an incomplete cubane-type framework;the eighth vertex
opposite W is vacant.The infrared spectrum of the complex shows bands at 2940(m), 1552(s),1468
(s), 1436 (m) 1377 (s) cm-1 characteristic of the 3,5-Me2pyrazole rings. The W-S stretching
frequency of [WOS3]2- in the complex (438 cm-1) is shifted to a lower frequency relative to that for
the free [WOS3]2- (470 cm-1, ammoniun salt). The 1HNMR spectrum of the complex consists of
singlet resonances at 2.23 ppm due to the protons of the 5C-CH3 and 3C-CH3 methyl groups. The
spectrum also exhibits a resonances at 5.99 ppm which is due to the protons in the H(4) position of
the four pyrazole rings. These results indicate that all of the pyrazole rings are equivalently bonded
to the copper atoms.
Keywords: Tungsten complexes, Polysulfide ions, Copper compounds
O-31
Synthesis and characterization of new nano thiocarbamate ligands and study of their
biological properties
Hafezeh Nabipour,* a,b Shahriare Ghammamy,a,c Shahriare Ashuri,d Mohammad Mirzaiea
a
Department of Chemistry, Islamic Azad University, Takestan Branch, Qazvin, Iran.
b
Member of Young Researchers Club, Islamic Azad University, Takestan, Iran .
(E-mail: [email protected])
c
Department of Chemistry, Faculty of Science, Imam Khomeini International of University, Qazvin,
Iran.
d
Department of Chemistry, Faculty of Science, University of Urmia, Iran.
The dithiocarbamate (DTC) ligands have also proven to be excellent compounds due to their
extensive applications as fungicides, pesticides, vulcanization accelerators [1]. Most of these
applications are based on complexation properties of DTC ligands with metal ions, especially with
transition metal ions [2]. DTC ligands readily form chelates with all transition metal ions through its
two donor sulfur atoms [3]. The secondary diamine ligands, used as starting material for the
preparation of the metal complexes, were obtained in 80% yield by condensation of 4methylbenzaldehyde or cinnamaldehyde with 1,6-hexamethylenediamine in methanol followed by
reduction of the Schiff base with NaBH4 in methanol. One-pot synthesis from this amine, carbon
disulfide, triethylamine and MCl2.6H2O (M = Ni, Co) gave colorless precipitates. The ultrasonic
treatment applied for preparation nanoparticles. The antibacterial activity of nanoparticles
derivatives tested against microorganism and compared with non-nano conditions. The resulting
nanoparticles were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR) and
transmission electron microscopy (TEM).
Key Words: Dithiocarbamate, Nano complexes, Ultrasonic, Biological activity
18
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O-32
Mechanistic and Spectroscopic Evidences for Multiple Active Oxidants in Mn(III)
Porphyrins Catalyzed Oxidation Reactions with Peroxomonosulfate
a
A. Naeimi, A. Rezaeifard*, M. Jafarpour, H. Raissi
Department of Chemistry, University of Birjand, Birjand, Iran
In this study, different factors that may affect the reactivity and selectivity of oxygenation of sulfide
to sulfoxide and sulfone using Peroxomonosulfate catalyzed by Mn-Pors in the presence of
nitrogenous axial bases as co-catalysts have been investigated. The oxidative activities of the
sulfides depend upon not only their stereoelectronic properties, but also they relate to the nature of
the Mn-Pors catalysts. The significant influence of protic solvents on the rate and selectivity of
oxidation reaction in particularly under the catalytic influence of electron-poor Mn-Pors has been
observed. When electron-deficient Mn-Pors were employed as catalyst, pyridines, demonstrated a
higher co-catalytic activity than N–H imidazoles. The sulfoxide/sulfone ratio obtained in the
oxidation of various sulfides in the presence of different Mn-Porphyrins, and also different oxidation
product distributions observed under the co-catalytic influence of different nitrogen donors along
with UV-Vis and especially Raman spectral data provide some evidences for participation of two
active species in the oxidation reactions using tetrabutylammonium peroxomonosulfate catalyzed by
Mn-Porphyrins.
Keywords: Porphyrin, Mechanism, Oxygenation, Active oxidants, Peroxomonosulfate, Raman.
O-33
Synthesis, characterization and crystal structure of dimethyltin(IV) coordination
polymers based on mixed bidentate liagnds
Ezatollah Najafi, Marzieh Vafaee, Mostafa M. Amini*, Hamid Reza Khavasi
Department of Chemistry, Shahid Beheshti University, Tehran 1983963113, Iran
The majorities of the organotin complexes with polymeric structure contains only single building
unit which can be classified as simple homo-coordination polymers. Organotin coordination polymer
with more than one building bulk appears to be limited. Among many ligands for assembly of mixed
ligands transition and main group metal coordination polymers, thiocynate has attracted attention
due to its particular symmetry and stereochemistry. In this work pyrazine carboxylic acid or 4,4'bipyridine lligands have been combined with thiocyanate as building bulk for preparation of
diorganotin coordination polymer containing pseudo-halide ligand.
The prepared organotin
coordination polymer, {[Me2Sn(C4H3N2COO)2]2[Me2Sn(NCS)2]}n (1) and [Me2Sn(NCS)Cl.(4,4'-bipy)]n
(2) have been characterized by NMR and IR spectroscopes in addition to elemental analysis. The
crystal structures of both organotin coordination polymers were determined by X-ray diffraction.
Complex 1 contains two independent tin atoms in which one of them is coordinated by two
bidenate pyrazine carboxylate ligands and the same time oxygen atoms of adjacent carboxylate
ligands coordinated to tin atom, and with two methyl groups in axial positions coordination number
raised to seven in form of a pentagonal bipyramidal geometry. The asymmetric unit in 2 contains
Me2Sn(NCS)Cl and 4,4'-bipy moieties and a 1D infinite rigid chain structure form through bridging of
the 4,4'-bipy ligand between tin atoms.
Keywords: Organotin, Coordination polymer, Single crystal structure
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O-34
Synthesis, Characterization and Crystal structure Determination of New Oxo-Centered
Trinuclear Iron(III) Acetate Complexes
Vahid Amani, Nasser Safari* and Hamid Reza Khavasi
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
Numeroueaus research work have shown that the interesting magnetic properties of the oxo
centered iron carboxylates are affected by R group in carboxylato, L ligand coordinated to the iron
and even conter-ion and solvent in the crystal lattice of them. However, some authors believe that
properties of the µ-oxo trigonal carboxylato metals are not strongly influenced by external packing
forces, but depend upon intrinsic electronic structure of the central cluster. [Fe3(µ3-O)(µOAc)6(py)3][FeBr4]2[py.H] complex (OAc is acetate) was prepared from reaction of FeBr3 with
pyridine in 1.2 molar aqueous HBr and 2.4 molar aqueous CH3COOH. Recrystallization of [Fe3(µ3O)(µ-OAc)6(py)3][FeBr4]2[py.H] in acetonitrile produced [Fe3(µ3-O)(µ-OAc)6(py)3][FeBr4] complex .
Both complexes were characterized by IR and 1H-NMR spectroscopies and their structures were
studied by single-crystal diffraction method. Hear we report the structure of the title complexes in
which counter ion has changed. Their solution behavior in the presence of different donor solvents
was studied by paramagnetic 1H-NMR
Keywords: Oxo-Centered; Trinuclear; Iron(III); Acetate; Pyridine; Crystal structure.
O-35
Oxygen Evolving Complex in Photosystem II: Better than Excellent
a
Mohammad Mahdi Najafpoura*
Institute for Advanced Studies in Basic
Sciences , Zanjan, Iran
The oxygen evolving complex (OEC) which induces the oxidation of water to dioxygen, is contain a
cluster of one calcium and four manganese atoms. may serve as a model to split water by sunlight.
The published data on structure of photosystem II provides a more detailed architecture of the
oxygen-evolving complex and the surrounding amino acids. We should use the detailed architecture
of the oxygen-evolving complex and learn some tricks from Nature to synthesize the nice catalyst
for water oxidation in artificial photosynthesis. In this paper, some new models for oxygen evolving
complex in photosystem II and a few tricks from Nature to oxidize water are introduced.
Keywords: Artificial Photosynthesis; Model complex; Photosynthesis, Oxygen; Water Oxidizing
Complex.
20
IICC12
O-36
Supramolecular assemblies of host–guest complexes of cucurbiturils with some organic
molecules: Cucurbit[8]uril-based fluorescent receptor for tryptophan
Ahmad Amiria, Mehdi Amirnasra, Paola Ceroni*b, Giacomo Bergaminib
b
Dipartimento di Chimica ‘‘G. Ciamician’’, Universita` di Bologna, via Selmi 2, Bologna, Italy.
(E-mail: paola.ceroni@ unibo.it)
a
Cucurbituril (CB), as a fascinating synthetic molecular receptor, features a hydrophobic cavity and
polar carbonyl groups surrounding the portals. It has been known that the varying cavity and portal
size lead to a remarkable affinity and selectivity toward guest molecules on the basis of
intermolecular interactions. Here, the formation of inclusion complexes between Mdap+ and
protonated HMdap2+ guest molecules with the cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8])
hosts has been investigated. We also studied the application of Mdap+@CB[8] complex as a
fluorescent receptor for tryptophan, due to the formation of Tryptophan●Mdap+@CB[8] 1:1:1
ternary complex. In summary, we have shown that the electron acceptor guest Mdap+ gives rise to
a very stable inclusion complex with CB[8], while leaving enough room inside the host cavity for the
formation of stable ternary complex with tryptophan. We monitored the formation of the ternary
inclusion complex using fluorescence emission measurements. In this regard, the fluorescence
emission of Mdap+@CB[8] is anticipated to be quenched by association with a π-donor molecule
such as tryptophan. These binding phenomena might be useful for the development of new
fluorescence methods to detect and quantitate tryptophan.
Keywords: Cucurbituril, Host-Guest, Fluorescence, Supramolecular Chemistry
O-37
Synthesis and characterization of hybrid complex of Ru (bpy)2Cl2 with Keggin
polyoxometalate and investigation of its electronic behavior
Zari Pahlevan Neshan, Majid Moghaddam*, Valiollah Mirkhani, Iraj Mohammadpoor-Baltork, Shahram
Tangestaninejad, Ahmad Reza Khosropour, Hadi Esfandiari
Department of Chemistry, University of Isfahan, Isfahan, 81746-73441 Iran
E-mail address: [email protected]
Polyoxometalates (POMs), as metal–oxygen cluster species, have obtained extensive attention due to
not only the structural diversity but also their attractive properties, such as catalytic activity
magnetism, photochemical activity and electrical chemistry. Keggin structure has general formula
[XM12O40]x-8 and lacunary Keggin is [XM11O39]n-. Hybrid complexes are combination of organi
and inorganic compounds that give new properties to them. Transition metal complexes have been
the subject of extensive electrochemical and spectroscopic studies, due to their excellent stability in
multiple redox states. Ruthenium complexes have found applications in a variety of fields and, in
particular, as photo-sensitizers in the conversion of solar energy into chemical or electrical energy
1,10-Phenanthroline-5,6-dione (Phen-dione) has extensive electronic delocalization and good
coordinating properties and in the synthesis of materials showing interesting optical or electrica
properties. These electron carriers can be readily injected and transported in Ru complexes. In thi
research a hybrid complex was prepared by the reaction of Ru(bpy)2Cl2 with a lacunary Keggin
Polyoxometalate such as α–K8SiW11O39 using 1,10-phenantholin-5,6-dione as a spacer. The prepared
hybrid complex was characterized by diffuse reflectance UV-Vis, FT-IR, cyclic voltametry (CV)
elemental analysis and X-ray diffraction techniques.
Keywords: Polyoxometalate; Lacunary Keggin; Hybrid complex; Ru complex.
IICC12
21
O-38
A series of new derivatives of tetradentate N2O2 type Schiff base ligands and their
oxovanadium(IV) complexes as highly efficient catalysts for the epoxidation of
cyclohexene
Jalal Rahchamania, Mahdi Behzada,*, Abolfazl Bezaatpourb and Vahdat Jaheda
a Faculty of science, department of chemistry, Semnan University, Semnan, Iran
[email protected]
b Department of chemistry, Faculty of science, Mohaghegh Ardabili University, Ardabil, Iran
A series of new derivatives of N2O2 type Schiff base ligands and their oxovanadium(IV) complexes
were synthesized and characterized by 1HNMR, IR and UV-Vis spectroscopies, cyclic voltammetry
and elemental analyses. The new ligands were derived from condensation of 4,5-dinitro-ophenylenediamine with 2-hydroxybenzaldehyde (4,5-diNO2Sal), 5-bromo-2-hydroxybenzaldehyde
(4,5-diNO2-5-BrSal), 3-methoxy-5-bromo-2-hydroxybenzaldehyde (4,5-diNO2-5-Br-3-OMeSal), 5nitro-2-hydroxybenzaldehyde (4,5-diNO2-5-NO2Sal), 5-methoxy-2-hydroxybenzaldehyde (4,5-diNO25-OMeSal),and 3-methoxy-2-hydroxybenzaldehyde (4,5-diNO2-3-OMeSal). The presence of electronwithdrawing groups in diamine moiety is regarded to increase the catalytic activity of the complexes
in epoxidation of alkenes. The new complexes were studied in epoxidation of cyclohexene using
tert-butylhydroperoxide (TBHP) as oxidant. Our results clearly showed that the new complexes are
highly efficient catalysts in this epoxidation process.
Keywords: Schiff Base; Oxovanadium(IV) Complex; Tetradentate Ligand; Catalyst; Epoxidation.
O-39
Preparation of complexes of [Cu(diamine)2Y]ClO4 with some ambidentate ligands,
characterization and X-Ray crystal structure
M. Ramezani and H. Golchoubian*
Department of chemistry, university of Mazandaran, Babolsar, Iran.
During the past decade, particular interest has been directed towards the investigation of copper(II)
complexes with pseudo halogens, due to their correlative structures and ability to show
choromotropism. In this regard, a series of mononuclear complexes of type [Cu(diamine)2Y](ClO4)
where diamine stands for N,N'-dimethyl,N'-benzyl-1,2-diaminoethane and Y= SCN−, OCN−, SeCN−
have been prepared and characterized on the basis of elemental analysis, molar conductance IR
and UV-Vis spectroscopies. The X-Ray crystal structure of [Cu(diamine )2OCN]ClO4 were determined
and revealed that the ambidentate ligand of OCN− is coordinated to copper(II) ion through N atom
and the copper(II) ion resides in a distorted square pyramidal environment. The comparison of the
IR spectra of the complexes with that of [Cu(diamine)2OCN]ClO4 demonstrated that all the
complexes have the same typical structures and the ambidentate ligands of Y are coordinate via Natoms. The solvatochromism behaviors of these complexes were studied by UV-Vis spectroscopy.
Keywords: Copper(II), Crystal structure, , Ambidentate ligand, Mono nuclear complex.
22
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O-41
Synthesis of Mg-Fe Layered Double Hydroxides nanostructure particles and Adsorption
of Azoic pigment on hydrotalcite-like compounds
K. Nejatia، M. Mansourfar*a ،Z. Rezvanib ، S. davaria
a
Payame Nour University, Tabriz , Iran
(e-mail: a*[email protected])
b
Department of chemistry, Azarbaijan University of Tarbiat Moallem, Tabriz ,Iran
In this work Mg-Fe-LDH was prepared by addition of a mixed aqueous solution of Mg(Cl)2 .6H2O
and Fe(Cl)3 .6H2O at a constant pH of 9.5 followed by subsequent hydrothermal treatment for 24h
in the mixture of water,1-propanol and surfactant (Ethylene glycol).This nanostructure particles is
well characterized by infrared spectroscopy, Scanning electron microscope (SEM) and X-ray powder
diffraction analysis. SEM images showed that the morphology of Mg-Fe-LDH is plate-like structure.
XRD analysis showed the formation of sharper and intense peaks, which might indicate the larger
crystallites size of LDH as well as higher crystallinity .The FT-IR spectra of LDH materials provide
many important information, especially about the interlayer anions and hence are very useful to
understand the structure of these materials. The effects of contact time, solution PH, temperature
and amount of YGX on YGX adsorption whit a fixed adsorbent dose (LDH) of 0. 5gL-1 were
investigated and determined by UV-Vis spectrophotometer. The results of adsorption experiments
indicate that the amount of YGX adsorption increases whit increasing amount of YGX and
temperature. The adsorption process was spontaneous and endothermic in nature and it supports
the surface heterogeneity of oxide surfaces.
Keywords: Nanostructure Particles, Layered Double Hydroxides, Hydrotalcite, Adsorption, Yellow
GX
O-42
Synthesis and characterization of new trans-1, 2-diaminocyclohexane schiff base ligand
containing azo group and its copper (II) complex
M. Saberinasab, H. Khanmohammadi*
* E-mail: [email protected]
The past few decades, have witnessed a great deal of interest in the chemistry of azo compounds
because of their versatile application in various fields such as dying textile fiber, biologicalpharmacological activities and advanced applications in organic synthesis. More over, utilizing and
function of azo dyes in electronic studies, has been subject of renewed curiosity. Besides, there
exist chief sorts of azo compounds, which was called azo schiffbase, consisting both azo and
azomethine groups. Azo-azomethine compounds play a prominent role in forming stable complexes
with transition metal ion due to their excel donor properties. In our ongoing investigations, a new
trans-1,2- diaminocyclohexane Schiff base ligand(H2L), derived by treatment of transe-1,2diaminocyclohexane and 1-(3-formyl-4-hydroxyphenylazo)-4-Nitrobenzene in ethanol solution. The
prepared azo ligand has been charectrized by 1H NMR, IR and UV-VIS spectroscopy. The following
Schiff base ligand has been used to prepare a new copper complex, synthesized by adding of the
appropriate metal salt to a hot solution of the ligand. The prepared complex was also characterized
by C, H, N elemental analyses, IR and UV-Vis spectroscopic methods.
Keywords: Schiff base; Azo-azomethine; Trans 1, 2-diaminocyclohexane; Copper complex
IICC12
23
O-44
Immobilization of cobalt phthalocyanin inside of MCM-48 mesoporous silica channels
as a highly selective heterogeneous catalyst for oxidation of olefin using H2O2 as an
environmentally friendly oxidant
Omid Sadeghi, Nasser Safari, Tahereh Ale’Mohammad, Mostafa M. Amini*, Maryam Adineh
Department of Chemistry,Shahid Beheshti University, G.C., Tehran, Iran
Unsubstituted cobalt phthalocyanines (CoPc) was immobilized into channels of MCM-48 mesoporous
silica, scheme 1, as a new and selective catalyst for oxidation of olefins. Catalytic activities of the
supported cobalt phthalocyanines for oxidation of cyclohexene to cyclohexanol or cyclohexanone
and also cyclooctene to epoxide (cyclooctene epoxide) by hydrogen peroxide as an environmental
friendly oxidant were studied in dichloromethane at room temperature. In this work external
surface of MCM-48 was coated with trimethoxymethyl silane and then inside of channels was
functionalized by N-[3-(triethoxysilyl)propyl]isonicotinamide (TPI) in order to immobilize cobalt
phthalocynanine only inside of channels by coordination to pyridine of TPI. Immobilization of
phthalocyanines has been confirmed by IR spectroscopy, X-ray powder diffraction in addition to
elemental analysis. XRD pattern confirmed that mesoporous structures of MCM-48 silica retained
after immobilization of cobalt phthalocyanine. This material has high potential as an industrial green
catalyst in oxidation of olefins to fine chemicals at room temperature. A schematic diagram of this
new modified mesoporous silica is shown below.
Keywords: Mesoporous Silica MCM-48, Phthalocyanine, Oxidation, Heterogeneous Catalyst
O-45
Synthesis, characterization and catalytic study of two oxo-peroxo tungsten(VI) and
molybdenum(VI) complexes with a tridentate Schiff base ligand in highly efficient and
selective oxidation of olefins with H2O2 as a Oxidant
M. Aminia , M. Bagherzadeha*
a
Chemistry Department, Sharif University of Technology, Tehran, Iran
A coordinated metal center activates hydrogen peroxide rendering peroxometal complexes, which
are important as intermediates in the substrate oxidation catalysis in homogeneous as well as
heterogeneous mode. A variety of synthesis of peroxocomplexes of various metals is known to
catalyze the oxidation of olefins, alcohols, and sulfides.In order to study the comparative catalytic
potentialities of the oxo-peroxo complexes of Mo and W, we report the synthesis, crystal structure
and catalytic activity of two oxidoperoxido tungsten(VI) and molybdenum(VI) with salicylidene
benzoyl hydrazineas as ligand in the epoxidation of olefins at room temperature with NaHCO3 as
cocatalyst and H2O2 as oxidant.The complexes show prolific catalytic activity in the hydrogen
peroxide oxidation of various olefins, to their corresponding epoxides.
Keywords: Oxidation, Olefins, Tungsten(VI), Molebdenum(VI), Oxo-peroxo
24
IICC12
O-46
Cytotoxic activity, Binding studies on interaction of novel anti-tumor palladium(II)
complex with calf thymus DNA
Maryam. Saeidifar 1, Hassan. Mansouri-Torshizi 1,* , Adeleh. Divsalar 2 and Ali.Akbar. Saboury 3
1
3
Department of Chemistry, University of Sistan & Baluchestan, Zahedan, Iran.
2
Department Of Biological Sciences Tarbiat Moallem University Tehran Iran
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran.
To reduce side effects Cis-Diaminedichloroplatinum(II) (cisplatin)1, a new anticancer complex of
formula [Pd(bpy)(pip-AA)]NO3 (where bpy is bipyridine and pip-AA is pipyridine amino acid) have
been synthesized and characterized. This complex have been interacted with DNA of calf thymus
using fluorescence, electronic absorption titration and gel filtration methods at 300K and 310K. The
complex shows 50% cytotoxic concentration (Cc50) value against chronic myelogenous leukemia cell
line, K562, much lower than that of cisplatin. The results of fluorescence titration suggest that the
above metal complex presumably intercalate into DNA. Gel filtration suggests them to bind with
DNA and the binding is strong and irreversible. There is a set of 7 binding site (g) for the complex
on the DNA with positive cooperativity in binding. n, the Hill coefficient (as a criterion of
cooperativity) find out to be 2.12 and 1.98 at 300K and 310K respectively. The above water soluble
compound denatures the DNA at very low concentration (~0.36 mM). Several binding and
thermodynamic parameters are also described by Uv-Vis technique.
O-47
Synchrotron X-Ray Powder Diffraction: Crystal Structure Determination of New
Phosphodiesterase Enzymes Inhibitor
A. R. Salimia, H. Eshtiagh-Hosseini*,a, H. R. Khavasi*,b, M. M. Aminib, and H. Sadeghianc
Department of Chemistry, Ferdowsi University of Mashhad, Mashhad 917791436, Iran
b
c
Department of Pharmacological, Mashhad University of Medical Sciences, Mashhad, Iran
a
Single crystal X-ray diffraction analysis is the usual way in the determination of structure of
crystalline solids. Nowadays, however, many materials such as pharmaceutical compounds cannot
be easily crystallized and exist only as powders. In these cases powder diffraction arises as an
alternative. Synchrotron radiation is the most powerful source of X-rays currently available for
powder diffraction experiments. In this study, we focused on structure determination of 6-(4-(4methylpiperazin-1-yl)-4-oxobutoxy)-4-methylquinolin-2(1H)-one as a phosphodiesterase (PDE)
enzymes inhibitor which improve cardiac contractility and may be used in congestive heart failure
(CHF) which is a major cause of death in patients with heart disease.
Key words: Structure Determination, Synchrotron, Powder Diffraction, Enzymes Inhibitor.
IICC12
25
O-48
Spectroscopic and Structural Studies of Some New C(O)NHP(O) Containing
Phosphorictriamides
A. Saneei *, M. Pourayoubi
Department of Chemistry, Ferdowsi University of Mashhad, Mashhad, 91779 Iran
New phosphoramidate compounds with formula XC(O)NHP(O)Y (Y = NHCH2C(CH3)2CH2NH and X
= CClF2 (1) & CF3 (2)) and X(O)NHP(O)Y2 (for X = CClF2, Y = NC4H8 (3), N(CH3)(CH2C6H5) (4),
NC4H8O (5), NHCH(CH3)2 (6), NHC6H4(4-CH3) (7), NHC6H11 (8), NHC6H5 (9), NHCH2C6H5
(10))) have been synthesized and characterized by IR, 19F NMR, 31P{1H} NMR, 31P NMR, 1H
NMR, 13C NMR. Moreover, the structures of compounds 1, 2 and 3 were determined by single
crystal X-ray determination. The P=O and P-N bond distances for these compounds are within the
values characteristic of analogous phosphorus compound. Therefore, the bond angles values show
that the P atom has a distorted tetrahedral configuration. The six-membered ring of the compounds
1 and 2 adopt a chair conformation and the P=O unit exist in equatorial position.
O-49
Porous Coordination Polymers: Homo and Hetero-Metal Structures Containing Pyrazine
and Pyridine Dicarboxylate Ligands
B. Notash, N. Safari* and H. R. Khavasi
The designing and constructing of porous coordination polymers (PCPs) or metal-organic
frameworks (MOFs) have attracted considerable attention owing to their potential as gas
storage/separation/sensor material, structural transformation abilities and other unique chemical
and physical properties. In recent years synthetic approaches for the creation of homo and hetrometal coordination polymers containing mercury as inorganic part and multi-dentate N,O-donor
ligands as organic part have been reported. In this study, we focused on the synthesis and
characterization of sodium, potassium and mercury coordination polymers with pyrazine-2,3dicarboxylic acid and pyridine-2,3-dicarboxylic acid and also mixed-metal (mercury-potassium)
which is shown in the Fig. 1. Complexes were characterized by spectroscopic methods as well as
single-crystal structure. The structural analysis shows that we have different structures from 1-D to
3-D coordination polymer which have shown porous structures and also hydrogen bonding and π-π
interaction.
Key words: Coordination Polymer, Mercury, Pyrazine, π-π Interaction
26
IICC12
O-50
Investigation of structural and biological properties of some metal oxides
nanoparticles prepared under ultrasonic irradiation
Fahmideh Shabania, Karimollah Gasemi Germi b*,Yashar Azizian c, Ali Khodayarid,
a
Department of Chemistry, Islamic Azad University, Young Researchers club, Ardabil Branch,
Ardabil, Iran
b
Department of Biology, University of Mohaghegh Ardabili, Ardabil, Iran
([email protected] or [email protected])
c
Physics Department, Institute for Advanced Studies in Basic Sciences(IASBS),Zanjan, Iran
d
Department of Chemistry, University of Mohaghegh Ardabili, Ardabil, Iran
In this research, M (OH)2 or 1 (M= Cu, Pb, Ag, Cd and Co) Nanoparticles have been prepared in
normal laboratory conditions via ultrasonic irradiation and after thermal treatment above to 200 oC
during 1 hour, nanoparticles transforms to M1 or 2O. Morphological and structural studies using
Scanning Electron Microscope (SEM) and X-ray diffraction (XRD) results shows that nanoparticles
have been formed in single phase crystals with the average size 5-50 nm which aggregated in the
form of nanoclusters with average size of 50-100 nm. These compounds after 72 hours showed
their cytotoxic effects on the stomach cancer cells cultured under certain conditions. For the growth
of cancer cells, some of doses of compounds also had inhibitor characteristics. The results are
completely new and provide new views for using of the mentioned compounds in chemotherapy.
Also Anti bacterial and anti oxidant properties nano particles studied and good results obtained.
Keywords: nano particles, metals oxide, cytotoxic, stomach cancer, Anti bacterial, anti oxidant.
O-51
Light Induced Control over the Optical and Morphological Properties of HydroxyphenylSubstituted Porphyrin Nanostructures
H. Shahroosvanda, N. Safaria*, E. Mohajeranib, T. Ale-mohammad a
b
Organic Material & Polymer Photonics Lab, laser Research Institute, Shahid Beheshti University,
Tehran, Iran
a
The design and construction of novel porphyrin architectures with well-defined geometries is an
area of increasing current interest. Among all methods, the deposition of porphyrins nanostructures
by irradiations has recently received much attention. In order to evaluate the role of various
irradiations in controlling the size, morphology and products, we investigated the behavior of a serie
of meso-substituted tetra phenyl porphyrin bearing hydroxyl peripherals group under UV and green
laser (532nm) irradiations. Properties of irradiated porphyrins were investigated by absorption and
emission spectra and AFM images. The power of UV lamp and green laser irradiations were about
20 W and 100 mW, respectively. The total irradiation time (t.t.) for all samples was
3600(s).Photodecomposition of the chlorinated solvent can occur during the irradiation with the UV
light, leading to the production of hydrochloric acid and, thus, to the formation of the porphyrin acid
derivatives. Porphyrin nanoparticles produced by green laser had well dispersibility and narrow size
distribution (about 7nm).Our results indicate that in irradiation experiments, the size and
morphology of the resulting porphyrin nanostructures strongly depend on the wavelength of the
source. Size and dispersity of the samples can be controlled through a careful choice of the light
source.
Keywords: Porphyrin Nanostructurs, UV irradiation, Green laser.
IICC12
27
O-52
Interaction of tetrakis(N,N′,N′′,N′′′-tetramethyl tetra-3, 4-pyridino) porphyrazine
copper (II) with anionic surfactant
a
Hamid Dezhampanaha,Esfandiar Alizadea,Bahram Ghalamia and Elham Shamsa*
Laboratory of Physical Chemistry, Department of Chemistry, Faculty of Science, University of
Guilan, , ,Rashat, Iran
(*e-mail:[email protected])
The interaction of a cationic water-soluble porphyrazine, tetrakis(N,N’,N”,N’’’ tetramethyl tetra-3,4pyridino)- porphyrazine copper(II) ([Cu(II) 3,4-tmtppa]4+) with anionic surfactant, sodium dodecyl
sulfate (SDS), sodium tetradecyl sulfate (STS) and sodium hexadecylsulfate (SHS) in aqueous
solution has been studied by optical absorption spectroscopy at 25 °C. The results show that [Cu
(II) 3, 4-tmtppa]4+ interact strongly with oppositely charged surfactant in the after micelle
concentration range that were changing soret band region of porphyrazine (hypsochromicity and
blue shift ) and the appropriate values of constant binding of dye-surfactant complex formation
were estimated. With increasing alkyl chain length of surfactants, the interactions become stronger,
which shows the importance of hydrophobic forces. Electrostatic interactions also play an important
role, as shown by the effect of NaCl on binding process.
Keywords: surfactant, porphyrazine, sodium dodecyl sulfate, spectroscopy.
O-53
Chelation of Cadmium by Combining Deferasirox and Deferiprone in rats
Amir Sh. Saljooghi*. S. Jamil. A. Fatemi. Faezeh Dahooee Balooch. Marzieh Iranmanesh.
Mohammad Reza Golbafan.
Chemistry Department, Shahid Bahonar University of Kerman, Kerman 76169, Iran.
The present research aimed to characterize the potential efficiency of two chelators after cadmium
administration for 60 days following two dose levels of 20 and 40 mg/kg body weight daily to male
rats. However, the hypothesis that the two chelators might be more efficient as combined therapy
than as single therapy in removing cadmium from the body was considered. In this way, two known
chelators Deferasirox (Exjade) and deferiprone (L1) were chosen and tested in the acute rat model.
Two chelators were given orally as a single or combined therapy for the period of a week. Cadmium
and iron concentrations in various tissues were determined by graphite furnace and flame atomic
absorption spectrometry methods respectively. The combined chelation therapy results show that
Exjade and L1 are able to remove cadmium ions from the body while iron concentration returned to
the normal level and symptoms are also decreased.
Key words: Chelation, Deferasirox, deferiprone, cadmium, iron
28
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O-54
Mechanistic studies of ligand fluxionality in [M(η5-Cp)(η1-Cp)(L)2]n
Elham S. Tabatabaie*a,Tahmine mehrabi a,shirin asar a,Mahshid moshtaghi a.elnaz khami a,Alireza
Ariafarda,b,
a
Department of Chemistry, Member of Young researchers club, Faculty of Science, Central Tehran
Branch, Islamic Azad University, Shahrak Gharb, Tehran, Iran
[email protected](Email:)
b
School of Chemistry, University of Tasmania, Private Bag 75, Hobart TAS 7001
Density functional theory has been used to provide a thorough investigation of the mechanistic
factors affecting Cp ligand fluxionality in a series of organometallic complexes, [M(η5-Cp)(η1Cp)(L)2]n, involving different metals, different oxidation states and different ligands. Excellent
agreement with experiment for the barrier heights for the 1,5-shift were obtained for the complexes
[Fe(η5-Cp*)(η1-Cp)(CO)2] and [Fe(η5-Cp)(η1-Cp)(CO)2] . For the range of complexes studied, the
barriers have been successfully rationalized in terms of hyperconjugation, metal-Cp bond strength,
and steric effects. In addition, the η1-η5 interconversion of the Cp binding mode is shown to be a
high-energy process, consistent with experimental observations. The L substitution reactions by η1Cp are quite sensitive to the nature of metal center and ancillary ligand. A detailed theoretical
explanation of the factors involved in all of these transformations is provided.
Keywords:1,5 shift; Fluxionality; Hyperconjugation; Reaction energy; Density Functional Theory
(DFT).
O-55
Effect of Alcohol Concentration on Size and Dispersion of Pt Nanoparticles Supported on
MWNTs
Z. Talaeia,*, A.R Mahjouba, M. M. Eskandarib and A.M. Rashidic
Department of Chemistry, School of Science, Tarbiat Modares University, Tehran, Iran
b
Chemistry and Petrochemicals Division, Research Institute of Petroleum Industry (RIPI), Tehran,
Iran
c
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran, Iran
a
There are many methods for the loading of platinum nanoparticles on carbon nanotubes including
dispersing a solution or suspension of solid support and reducing the metal atoms to activate the
catalyst. Most popular methods were known by adding reducing agents such as HCHO, HCOOH,
NaBH4, and N2H4. In this work a new method of synthesis of highly dispersed Pt nanoparticles with
large catalytic surface area on multi-walled carbon nanotubes in low temperatures and short times
under high-intensity ultrasonic field was developed. A variety of Pt/MWNTs catalysts were prepared
from an alcoholic solution of H2PtCl4 in the presence of carbon nanotube by adding a small amount
of inorganic salts as stabilizer and dispersant.The effect of alcohol concentration on Pt particles size
and distribution were investigated. MWNTs products were characterized by X-Ray diffraction
(XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman
spectroscopy. The results showed that by altering alcohol concentrations Pt nanoparticles were
uniformly dispersed on the MWCNT surface.
Keywords: Multiwalled Carbon Nanotube, Platinum Nanoparticles, Dispersion.
IICC12
29
O-56
Comparison of optical properties of zinc oxide with different morphology
Maryam Movahedia, Ali R. Mahjoub*b, Akram Hosseinianc and Maryam Afsharpourd
Chemistry Department, Payame Noor University (PNU), PO. Box. 81395-671, Isfahan Iran.
b
Chemistry Department, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran
c
Department of Engineering Science, University Colleges of Engineering, University of Tehran, Iran
d
Nanoscience and technology research center (NSTRC) - University of Tehran, Tehran, Iran
a
Zinc oxide is of great interest for photonic applications, and dust, the optical properties of different
forms of zinc oxide, single crystals, thin films and powder have been extensively studies. In this
work, we used the photoluminescence and UV spectroscopy as effective methods for evaluating
optical properties of zinc oxide with different morphology. The photoluminescence spectra of the
samples were measured by an excitation wavelength of 325 nm at room temperature. Results show
that, the violet, blue and green emissions due to the defects produced during the synthesis.
Generally, the UV peak is due to the recombination of photo generated electrons and holes. Zinc
oxide absorbs light below a threshold wavelength λg, the fundamental absorption edge which is
related to the band gap energy via λg (nm) = 1240 / Eg . The absorption edge and the band gap
energy were calculated for samples about 3.10-3.26 ev. In summary, the size, morphology and new
synthetic strategies of zinc oxide have great influences on their optical properties.
Keywords: Zinc oxide, Optical properties, Photoluminescence, Band gap
O-57
A new insight on characteristics of bridged B-H-B protons: theoretical studies on
interaction of B2H6 with some hydrogen bond acceptor molecules
A. Zabardasti
Department of Chemistry, Lorestan University, Khoramabad, Iran
E-mail: [email protected]; Tel/fax: +98-661-2200185
Ab initio calculations were used to analyze the interactions between bridged protons (B-H-B, Hb) of
B2H6 with NH3, NH2Me, NHMe2, NMe3, H2O, MeOH, OMe2, HCN, MeCN molecules at the MP2/6311++G(d,p) computational level. Diborane has two types of terminal (Ht-B) and bridging (B-Hb-B)
hydrogen atoms which they are different in their nature and characteristics. The bridged hydrogens
of B2H6 due to participation in electron deficient ‘three-center, two-electron bonds’ bearing partial
positive charges and could act as hydrogen bond donor (HBD) toward electron donating molecules
which they act as hydrogen bond acceptor (HBA).1 These interactions results to Hb…X (X= N, O)
hydrogen or Hb…H dihydrogen bond. Topological analysis of the electron density of obtained
structures have been carried out using the Atoms in Molecules (AIMs) methodology.
Stability of these complexes are close together and are in the order B2H6-NH3 〈 B2H6-NH2Me 〈 B2H6NHMe2 〈 B2H6-NMe3. This order of stabilities are in agreement with basicity of related amines.
Similarly, for Hb...O complexes the order of stabilities was predicted as B2H6-OH2 〈 B2H6-OHMe 〈
B2H6-OMe2. Also our results show that stability of B2H6-NCCH3 is slightly greater than B2H6-NCH
complexes.
Keywords: B2H6, bridged protons, hydrogen bond donor, hydrogen bonding
30
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O-58
Enhanced Reactivity and Stability of cis-Dioxomolybdenum Complexes with Electrondeficient and Bulky Tridentate Schiff Base Ligands
N. Monadi,a,b A. Rezaeifard,a* I. Sheikhshoaeib
b
Department of Chemistry, , Shahid Bahonar University of Kerman, Kerman, Iran
a
The oxotransfer chemistry of molybdenum has been of great interest for the last two decades.
Molybdenum has a special place in this context since the active sites of enzymes like nitrogenase,
nitrate reductase, aldehyde oxidase, sulfite oxidase and DMSO reductase normally have a
molybdenum center coordinated to N, O, S donor sets of ligands. The oxotransfer model reaction
has attracted much attention in recent years due to its biological relevance to understanding the
structure–function relationships of these enzymes. In this work the synthesis of novel Mo(VI)complexes containing asymmetric ONO tridentate Schiff base ligands have been described. A highly
efficient epoxidation method using TBHP activated by these simple Mo(VI)-complexes in desired
times with excellent chemo- and stereoselectivity has been developed. The electron-poor (MoX) and
bulky groups (MoY) on the salicylidene ring of ligand promoted the effectiveness of the catalyst.
The relative high TOF and TON obtained in the epoxidation of alkenes, along with good/high
percentage of the remaining catalysts at the end of the reactions, confirmed clearly the high activity
and also relative stability of Mo-catalysts towards oxidative degradation.
Keywords: Dioxomolybdenum, hydroperoxide, Epoxidation, Schiff base, Stability.
O-59
Synthesis and investigation of catalytic activity of molybdophosphoric acid
encapsulated into Y zeolit (Host-Guest system) as a efficient catalyst for Solvent-free
synthesis and Deprotection of 1,l-Diacetates
Maryam Moosavifar1*, Shahram Tangestaninejad2, Majid Moghadam2, Valiollah Mirkhani2, Iraj
Mohammadpoor-Baltork2
1
Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
2
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan, Iran
A mild and efficient procedure has been developed for the synthesis of acylals from aldehydes and
anhydride acetic in the presence of molybdophosphoric acid encapsulated into dealuminated zeolite
Y (MPA-DAZY) as a catalyst under solvent-free conditions at 45-55°C in good yield. The
deprotection of acylals has also been attained using this catalyst in acetonitrile. The Catalyst was
reused several times without efficient loss of its catalytic activity.
Keywords: MPA-DAZY, protection, deprotection, 1,1- diacetates, solvent-free.
IICC12
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O-60
Synthesis, Characterization and X-ray Structures of Two Novel Pb(II) Coordination
Polymer and Coordination Compound with Bipyridine Derivative Ligands
a
R. Alizadeha*
School of Chemistry, Damghan University, Damghan, Iran
*
The rational design and synthesis of novel coordination polymer is of current interest in the field of
supramolecular chemistry and crystal engineering and recently much attention is given to 2,2′bipyridine (bpy) moiety in coordination and metallosupramolecular chemistry, because of its high
binding affinity for a variety of metal ions and photophysical, photochemical, and electron transfer
properties of bpy-metal complexes. Present work is related to two novel Pb(II) complexes (1,2)
with bipyridine derivative ligands. These complexes were synthesized from the reaction of Pb(NO3)2
with 5,5′-dimethyl-2,2′-bipyridine (1) and 6,6′-dimethyl-2,2′-bipyridine (2) ligands. Both complexes
were thoroughly characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy and singlecrystal X-ray diffraction methods. The unit cell dimensions for (1) are: a = 8.5929(11) Å, b =
16.0434(17) Å, c = 11.0932(15) Å and β = 97.630(10)º and for (2) are: a = 18.117(2) Å, b =
10.2162(9) Å, c = 8.6536(11) Å and β = 112.000(9)º. According to the X-ray structure data, (1) is
a coordination polymer of lead(II), while (2) is a monomeric lead(II) complex.
Keywords: Crystal Structure, Pb(II), Coordination Polymer, 5,5′-Dimethyl-2,2′-bipyridine, 6,6′Dimethyl-2,2′-bipyridine.
O-61
Synthesis, Characterization and Investigation of Catalytic Activity of a New OrganicInorganic Hybrid Keggin polyoxometalate
M.J. Bagi, R. Fazaeli* and H. Aliyan
Department of Chemistry, Islamic Azad University, Shahreza Branch, 86145-311, Iran.
The interest in design, synthesis and characterization of organic–inorganic hybrid materials has
been growing extensively. One approach for design of hybrid material is to introduce some
transition metal complexes (TMCs) into the backbone of inorganic oxides. The TMC can dramatically
influence the inorganic oxide microstructures. Recently, polyoxometalates (POMs) have been
employed as inorganic building blocks for construction of organic–inorganic hybrid materials
because of their interesting magnetic, electrical and optical properties, while the organic
components are generally composed of organic amines as structural directors. Hydrothermal
technique is an effective approach for the preparation of hybrid materials, and many examples of
polyoxoanion-supported TMCs including mono-supported, bi-supported, tri-supported, and tetrasupported, have been reported. The aim of our work is to study hybrid materials based on POMs
possessing coordination abilities and interesting magnetic, electrical and optical properties. we have
recently prepared successfully new POM supported TMCs, [Cu(DAP)2]2[SiW12O40] is constructed
from Keggin heteropolyoxoanions and copper complex fragments.
Keywords: organic-inorganic hybrid, hydrothermal conditions, polyoxometalates (POMs)
32
IICC12
O-63
Thermodynamic investigation of copper (II) 4, 4’, 4”, 4’”- tetrasulfonated
phthalocyanine with calf thymus DNA
a
H. Dezhampanaha, and T. Darvishzad a*.
Department of Chemistry, Faculty of Science, University of Guilan,
(E-mail:[email protected])
Binding properties of copper (II) 4, 4’, 4”, 4’”- Tetrasulfonated phthalocyanine (Cu(tsPc)4-) in the
presence of various concentration of calf thymus DNA (ct-DNA), has been studied in 7.5 mM
phosphate buffer, pH = 7.2 and at various temperatures by UV-vis absorption. The results show
that Cu(tsPc)4-does not have any affinity for aggregation due to increasing of salt concentration and
exists as monomers even in homogeneous aqueous solutions of high ionic strengths (more than 2M
NaCl). Interaction of Cu(tsPc)4-with calf thymus DNA has been also studied in 1mM aqueous
phosphate buffer of pH 7.2, by optical absorption . The appearance of hypochromicity of less than
30% and bathochromicity shift of ∆ λ ≤ 3 nm in UV-vis spectra of (Cu(tsPc)4- of phthalocyanine
due to interaction with DNA, via the metal in the central core of phthalocyanine . The binding
constant (K) was obtained by analysis of the optical absorption spectra of the complex at various
DNA concentrations using datan software. The value of K was estimated to be 6.02 × 105 ± 0.06
M-1 at 25˚C. The thermodynamic parameters were calculated by vanُ t Hoff equation. The enthalpy
and entropy changes were -111.43 ± 3.28 kJ/mol and 265.19 ± 9.88 J/mol.K at 25˚C,
respectively. The data indicate that the process is exothermic and enthalpy, entropy driven
suggesting that electrostatic and hydrophobic forces play a considerable role in the interaction
process.
Keywords: phthalocyanine, thermodynamics of binding, optical absorption, DNA
IICC12
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33
P-1
Synthesis, Characterization and Crystal structure determination of Cobalt (II) and (III)
complexes containing, bipyridine derivatives
Niloufar Akbarzadeh Torbatia, Ali Reza Rezvani*a ,Hamideh Saravani, Nasser Safarib, Vahid
Amanib
a
Department of Chemistry, University of Sistan and Baluchestan,P. O. Box 98135-674, Zahedan,
Iran
b
Department of Chemistry, Shahid Beheshti University G. C., 1983963113, Evin, Tehran Iran
Although ligands having nitrogen as a donor atom are by far the most extensively studies, interest
in 2,2´- bipyridine and derivatives donor chelating agents have grown over the years and the
number of chemical studies in this area has increased considerably. These ligands have been
extensively used as a metal chelating ligand due to its robust redox stability and ease of
functionalization. Here we describe the structural chemistry of the hindered polypyridyl ligands
such as 6- methylbipyridine (6-mebpy), 6,6´-dimethylbipyridine (6-6´dmbpy), and 5,5´dimethylbipyridine (5,5´-dmbpy) highvalent cobalt precursors. This complexes have different
coordination numbers and configurations such as tetrahedral for coordination number four and
octahedral for six. Three new Co(II) and Co(III) complexes [Co(5,5´-dmbpy)3]Cl3.CH3CN.2H2O (1),
[Co(6-mbpy)Cl2] (2) and [Co(6-6´dmbpy)Cl2](3) where 5,5´-dmbpy= 5,5´-dimethyl-2,2´-bipyridine,
6-mbpy = 6-methyl-2,2´-bipyridine and 6-6´dmbpy= 6,6´- dimethyl-2,2´-bipyridine were
1
synthesized and characterized by The elemental analysis, IR, UV–Vis, CV, H NMR and 13C NMR
spectroscopies. The cyclic voltammetry study in DMSO and methanol gave all the expected waves
for the redox processes of the metal Co(II) and the ligands. The X-ray diffraction study of
compounds 1, 2 and 3 verified their analogous proposed octahedral arrangement of the ligands
around the cobalt(III) for 1 and tetrahedral arrangement of the ligands around the cobalt(II) for 2
and 3. The complex 1 is low spin with a spin multiplicity of 0 and complexes 2 and 3 are high spin
with a spin multiplicity of 4.
.
Keywords: 5,5´-dimethyl-2,2´-bipyridine, 6,6´- dimethyl-2,2´-bipyridine, 6-methyl-2,2´-bipyridine
P-2
Synthesis, Characterization and Crystal structure of Tetrahedral Cobalt(II) complex
with 2,2'-biquinoline ligand
Amanib
a
Iran
b
2,2'-Biquinoline (abbreviated as biq) and its derivatives owing to their strong photoluminescence
and electroluminescence properties are widely used in various thin film application devices system
to mimic photosynthetic light harvesting. Bidentate ligand 2,2'-biquinoline (biq) with steric
hindrance substituents cis to the nitrogen atoms has been used in the synthesis of transition metal
complexes. Thetrahedral complex Co(biq)Cl2 has been synthesized and characterized by IR, UV/vis,
CV and single crystal X-ray diffraction analysis. Violet crystals of [Co(biq)Cl2] were grown by
methanol diffusion into an dimethylformamid solution of the complex. This complex has a
monoclinic crystal system (Z=4) and space group of P21/n with a = 7.9925(10) Å, b = 12.2108(8)
Å, c = 16.8030(19) Å, β = 102.617(9) °, and V = 1600.3(3) Å3. The structure was refined by using
13850 independent reflections, with I>2σ (I) to an R factor of 0.0373. The X-ray diffraction study of
this compound verified their analogous proposed tetrahedral arrangement of the ligands around the
cobalt(II) atom.
Keywords: 2,2'-Biquinoline, Bidentate, Thetrahedral complex, monoclinic
34
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P-3
Synthesis, characterization and crystal structure of new four-coordinated
cobalt(II) complexes containing phenanthroline derivatives
Amanib
a
Iran
b
The first row transition metal complexes containing these polypyridyl ligands not only have
important biological properties, but also have gained importance of their versatile roles as building
blocks for the synthesis of metallo-dendrimers, as molecular scaffolding for supramolecular
assemblies, catalysis, electrochemistry and ring-opening metathesis polymerization. Depending to
the nature and the size of ligands, the divalent cobalt complexes have different coordination
number and configurations such as square planar and tetrahedral for coordination number four,
square pyramid and trigonal bipyramid for five and finally octahedral for six. Two new tetrahedral
Co(II) complexes [Co(dmphen)Cl2)] and [Co(ph2dmphen)Cl2]2.CHCl3, (where dmphen=2,9-dimethyl1,10-phenanthroline
or
neocuproin
and
ph2dmphen=
2,9-dimethyl-4,7-diphenyl-1,10phenanthroline or bathoneocuproin were synthesized and characterized by the elemental analysis,
1
IR, UV–Vis and H NMR spectroscopies. The single crystal X-ray diffraction study of two compounds
verified their analogous proposed tetrahedral arrangement of the ligands around the cobalt(II) ion.
Measurment of magnetic susceptibility (χ =2.35×10-5) by the 1H NMR (Evans method) gives the
magnetic moment of 4.35 BM, and this also supports the tetrahedral structure of the complex with
S=3/2.
Keywords: transition metal, polypyridyl ligands, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl4,7-diphenyl-1,10-phenanthroline
P-4
Effect of reduction temperature on catalyst for slurry Fischer–Tropsch synthesis
Ali A. Mirzaeia, F. Karimia, I. Rezazadeh Fallah-Anaria, M. Sahebi-Shahemabadia
a
Department of Chemistry, University of Sistan & BaluchestanZahedan, Iran
E-Mail: [email protected]
Fischer-Tropsch synthesis (FTS) as an alternate method for synthesizing liquid fuels and chemical
feed-stocks from syngas derived from coal, natural gas, and other carbon sources, has drawn
renewed attention in recent years. FTS produces a mixture of hydrocarbons and oxygenates, and
the hydrocarbons are the main products, which range from methane to heavy wax. The conditions
for the pretreatment of the iron-based catalyst used for FTS have significant effects on its activity
and selectivity. It has been well documented that H2, CO or syngas can be used as reductive agent
during the pretreatment. The iron phase compositions of catalysts reduced with syngas were
strongly dependent on pretreatment conditions employed. The effect of reduction temperature on
catalyst was characterized after reduction at different temperatures and time of reduction under
conditions relevant to operation (temperature, 200-450◦C; pressure, 1 bar; H2/CO feed molar ratio,
2–1, time of reduction: 2-10 hours). A fixed-bed micro-reactor was used with an Iron-manganese
oxide catalyst prepared by a Sol-gel method. Pretreatment with syngas at lower temperature
prevents iron catalyst activation. With the increase in the reduction temperature, the product
distribution shifted towards the lower molecular weight products.
Keywords: Fischer-Tropsch synthesis, Iron-manganese oxide, Sol-gel, reduction temperature
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35
P-5
Synthesis, characterization and computational study of a novel triple Carbon-Carbon
bonded organotin(IV) complex
a
Fatemeh Tavakoliniaa,*, Mohammad Yousefia
Azad university, Shahre-Rey branch, Tehran, Iran
Organotin compounds are organometallic compounds with vast industrial and agricultural
applications. These compounds have varying degrees of toxicological properties, depending on the
nature and number of alkyl groups bonded to the tin atom. A new organotin carboxylate complex
have been synthesized by the reaction of phenyl acetylene carboxylic acid (HL) with dimethyltin
dichloride. HL was dissolved in ethanol. Sodium ethoxide, prepared by dissolving equimolar Sodium
in ethanol was then added to it. The resulting mixture was refluxed with constant stirring for 1 h
under Argon atmosphere at 60˚C. A hot ethanolic solution of Me2SnCl2 was added to the solution of
sodium salt of the ligand in 1:2 molar ratio. The resulting mixture was further refluxed with
constant stirring for 4-5 h, and was then filtered to remove sodium chloride formed. The melting
point of the crystalline product was 198-199˚C. The complex was characterized by elemental
analysis, IR and 1HNMR. Furthermore the computational study carried out for comparison of
theoretical and experimental data. On the whole coupling constant value (81 ppm) of 1HNMR
suggested hexacoordinated structure, according to this we predict л-back bonding from triple bond
of acetylene to central Tin metal.
Keywords: Organotin complex, Phenyl acetylene carboxylic acid, Organometallic compound, лBack bonding
P-6
Synthesis and characterization of some supra molecules of organotin compounds and
kryptofix5
a
Fatemeh Tavakoliniaa,*, Mohammad Yousefia
Azad university, Shahre-Rey branch, Tehran, Iran
Cryptands (trade name of kryptofix) are cyclic or polycyclic molecules which contain three or more
binding sites held together by covalent bonds. These molecules are three dimentional analogues of
crown ethers. These complexing agent display a wide range of binding specificities. Two novel
methyltin complex of kryptofix5 have been synthesized. Me2SnCl2(Kry) compound was prepared by
dissolving both metal and ligand in ethanol and dropwise addition of kryptofix5 to dimethyltin
dichloride. The reaction mixture was stirred 12 h and product as a precipitate isolated. Melting
range of the complex was 173±2˚C. [Me2Sn(OCOCF3)2(Kry)] compound was prepared by addition
of CF3COOAg in to a metanolic solution of Me2SnCl2 in 2:1 molar ratio. The AgCl precipitate was
removed and the metanolic solution of Kryptifix was added to filtrate. The reaction mixture was
stirred about 48 h, so the product isolated as a precipitate. The melting range of the complex was
117±2˚C. The synthesized complexes were characterized by FT-IR, NMR and Mass spectroscopies.
Keywords: Organotin(IV), Supra molecule, Kryptofix, Dimethyltin dichloride.
36
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P-7
Synthesis, spectral properties and thermal analysis of Zn(II) complexes with Schiff
bases derived from β-alanine
a
R. Abbasi-Hormozia,* and T. Sedaghatb, M. Kootib
Department of Chemistry, Science and Research Branch, Islamic Azad University of Khouzestan,
Ahvaz, Iran
b
Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz, Iran
Aminoacid Schiff bases and their transition metal complexes have recently received considerable
attention due to their biological properties including fungicidal, bacterial and antiviral activity.
Transition metal complexes of salicylaldehyde aminoacid Schiff bases are possible model
compounds in toxicological investigations. The amino acid Schiff bases are moisture sensitive and
evolve the aldehyde on exposure to air. Complexation with metals stabilizes the Schiff base to some
content. As a rule these complexes are obtained by template synthesis. Although the metal
complexes of amino acid derivatives have been investigated extensively but less works are devoted
to complexes with β-aminoacid Schiff bases particularly with β-alanine. In view of the important role
of zinc in biological systems, in this research work three Zn(II) complexes were synthesized by
reaction of aldehydes (5-Bromo-2-hedroxybenzaldehyde, 2-hydroxynaphtaldehyde and o-vanilin)
and β-alanine with Zn(II) acetate salt in situ using the autocatalytic action of Zn(II) ion. The
complexes were characterized by UV-Vis, FT-IR and 1HNMR spectra and thermal analysis. On the
basis of these data, the Schiff base was coordinated to metal as tridentate dianionic one via
phenolic and carboxylate oxygen and azomethine nitrogen. The coordination sphere is completed
by one water molecule.
Keywords: Aminoacids, Schiff base, Zn(II) complexes, Thermal analysis
P-8
Iron complex immobilized on silica as effective heterogeneous catalyst in oxidation of
olefins with hydrogen peroxide
a
Vahideh Abbasi and Hassan Hosseini Monfareda, *and Alireza Aghaeib
Department of Chemistry, Zanjan University 45195-313, Zanjan, Islamic Republic of Iran.
b
Materials and Energy Research Center, 14155-4777, Tehran, Iran.
The catalytic epoxidation of olefins has been a subject of growing interest in the production of
chemicals and fine chemicals since epoxides are key starting materials for a wide variety of
products. Recovery and recycling of homogenous transitions metal catalysts are the major
drawbacks for their industrial use in catalysis. To overcome this difficulty several studies have been
done to immobilize homogeneous catalysts on different organic or inorganic supports. Supported
iron catalysts are active in a wide range of applications. In this study a new iron-hydrazone complex
was synthesized and immobilized on silica surface by use of a covalent linkage. We have found that
as synthesized iron catalyst was able to catalyze epoxidation of various olefins with the
environmental friendly oxidant such as H2O2. The heterogeneous iron catalyst was stable, efficient
and resulted to high conversion olefins to the corresponding epoxides.
Keywords: Iron complex, Silica, Heterogeneous catalyst, Olefins, H2O2.
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37
P-9
Synthesis and Characterization of New Macroacyclic Schiff base Complexes from
Potentially Hexadentate Ligand (N2O4) in the Presence of some Transition
Metal ions
a
H. Goudarziafshar*, a M. Nikoorazm, a A.Ghorbani Choghamarani, b H.keypour and a Y. Abbasi
a
Department of Chemistry, University of Ilam, Ilam, Iran
b
Faculty of Chemistry, University of Bu-Ali- Sina , Hammadan,Iran
The condensation of primary amines with carbonyl compounds yields Schiff bases. In the recent
years, there has been considerable interest in the chemistry of transition metal complexes of Schiff
bases. This is due to the fact that Schiff bases offer opportunities for inducing substrate chirality,
tuning the metal centred electronic factor, enhancing the solubility, and stability of either
homogeneous or heterogeneous catalysts. Schiff bases have been extensively employed in the
understanding of molecular processes occurring in biochemistry, catalyst, material science,
activation, encapsulation, transport and sepration phenomena, hedrometallurgy, etc. In this work,
we report the synthesis of a new symmetrical potentially hexadentate (N2O4) Schiff base
macroacyclic complexes [ML]2+ derived from the reaction of 2,2'-(propane-1,3diylbis(oxy))dibenzenamine (L1 ) that was synthesized by the modified method of Cannon et al with
salicylaldehyde ( L2 ) in the presence of M2+ (Cd2+, Mn2+) as template agent . The structure of the
ligand and its complexes was investigated using FT-IR, 1H and 13C NMR, mass spectra
measurement.
Keywords: Schiff base ligands, Metal complexes, Macroacycles, Template effect
P-10
Synthesis and characterization of some new 2-amino-3-hydroxypyridine Schiff base
compounds and their interactions with metal ions
Marzieh Abdeshah and Khosro Mohammadi*
Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran
E-mail: [email protected]; [email protected]
Schiff bases and their metal complexes have been synthesized and characterized because Schiff
bases are able to stabilize different metals in various oxidation states, controlling the performance
of metals in a large variety of useful catalytic transformations. Enolic Schiff-base ligands prepared
from acetylacetone and related β-diketones with mono- or diamines have attracted much attention
in recent years. Because of their distinct advantages such as ease of synthesis, low cost as well as
variety of coordination sites via different β-diketones and amines, they have been very important
subject of coordination chemistry. In this study, we reported the synthesis of some new Schiff base
compounds from 2-amino-3-hydroxypyridine with acetylacetone and related β-diketones. The
compounds were characterized by 1H NMR and IR spectroscopy. Then, the interactions of Schiff
base ligands with metal ions were studied.
Keywords: Schiff base; 2-Amino-3-hydroxypyridin; Acetylacetone; Complex.
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P-11
Photocatalytic degradation of new azo-azomethine diaminomaleonitril-based ligands by
ZnO nano particle under UV irradiation
Aliyeh Abdollahi ,Hamid Khanmohammadi
Department of Chemistry, Arak University, 38156 Arak, I. R. Iran
In recent years, problem of wastewater containing highly toxic and refractory chemicals became
very important. Azo dyes are common industrial pollutants, the removal of these compounds from
wastewater is very necessary task. Due to the stability of azo dyes, there is a need to develop
treatment methods in eliminating dyes that semiconductor-assisted photocatalysis among the
advanced oxide processes (AOP) has attracted the public concern for its ability to convert the
pollutants into the harmless substances directly in the wastewater. Further more employing nanosized metal oxids as catalysts have been caused to enhance the degradation efficiency. In the
present work, we were synthesized a new azo-azomethine diaminomaleonitrile-based ligand, HLn
(n=1,2), by monocondensation reaction of diaminomaleonitrile and 5-(4-R-phenyl)-azosalicylaldehyde (R:Cl, Et) in ethanol. The photocatalytic activity of ZnO nano particle for degradation
of the prepared ligands in the present of UV irradiation and H2O2 has been studied. The results
showed the combination of oxidant (H2O2) with a photocatalyst (ZnO/UV) has the high capability of
oxiding the prepared compound.
Keywords: azo dyes; degradation; photocatalysis; nano particle
P-12
Synthesis and characterization of a new azo-azomethine diaminomaleonitrile-based
ligand and its Ni(II) complex
a
Aliyeh Abdollahi,Hamid Khanmohammadia
Department of Chemistry, Arak University, 38156 Arak, I. R. Iran
Azo–azomethine compounds and their metal complexex attracted much attention because of their
electronic structure features and coloring properties [1,2]. Among the plethora of azo dyes, those
containing diaminomaleonitrile, DAMN, are of particular interest [3,4 ]. The azomethine derivatives
of DAMN are important as synthetic intermediates and they are also used in dye synthesis. Their
great potential has recently been demonstrated in the synthesis of conjugated linear polymers and
in the thermostable optical material industry. Most reaction methods for synthesis of azomethine
derivatives of DAMN described to date involve the use methanol as a solvent without catalysts, but
ethanol and acid catalysis are required if the aldehyde bears a strong electron-withdrawing group .
We report here the synthesis and characterization of new acyclic azo-azomethine
diaminomalenitrile-based ligands, H2L. The ligand was prepared by monocondensation reaction of
2,6-bis(N-(2-amino-(z)-1,2-dicyanoetheneimino))-4-methylphenol), L, with 5-(4-NO2-phenyl)-azosalicylaldehyde in acetic acid. The prepared azo ligands have been characterized by elemental
analysis, IR, UV-vis and NMR spectroscopices. A new acyclic complex of Nickel(II) was also
prepared by reaction of H2L and Ni(II) ion in THF. The prepared complex was characterized by
microanalysis data, IR, and UV-Vis spectroscopy.
Key words: azo-azomethin; diaminomaleonitril; conjucate; monocondensation
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P-13
Highly efficient and chemoselective trimethylsilylation of alcohols and phenols with
hexamethyldisilazane (HMDS) catalyzed by electron-deficient vanadium(IV)porphyrin
S. Abdolmanf Taghavi, M. Moghadam*, I. Mohammadpoor-Baltork, S. Tangestaninejad, A. R.
Khosropour, Valiollah Mirkhani
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan, Iran 81746-73441
*E-mail address: [email protected]
Protection of hydroxy functional groups by their conversion to silyl ether groups is a common and
often used method in synthetic organic chemistry. The protection of such functional groups is often
necessary during the course of various transformations in a synthetic sequence, especially in the
synthesis of fine chemicals and natural products. Silylation with HMDS is nearly neutral, does not
need special precautions and produces ammonia as by-product. However, the main disadvantage of
HMDS is its poor silylating power in the absence of a suitable catalyst which needs forceful
conditions and long reaction times in many cases. Therefore, a catalyst is needed for accelerating
this reaction. In this paper, rapid and highly efficient trimethylsilylation of alcohols and phenols with
hexamethyldisilazane (HMDS) in the presence of catalytic amounts of high-valent [VIV(TPP)(OTf)2] is
reported. This catalytic system catalyzes trimethylsilylation of primary, secondary and tertiary
alcohols as well as phenols, and the corresponding TMS-ethers were obtained in high yields and
short reaction times at room temperature. It is noteworthy that this method can be used for
chemoselective silylation of primary alcohols in the presence of secondary and tertiary alcohols and
phenols.
Keywords: Alcohol; Phenol; Trimethylsilyl ether; Hexamethyldisilazane; High-valen V(IV) porphyrin
P-14
Synthesis and spectral characterization of some new Carbacylamidophosphate
derivatives
F. Abdevali, Kh. Gholivand, S. Farshadian and R.Rahimi
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
The chemistry of Carbacylamidophosphates which have –C(O)NHP(O)- in their molecular core units
are recently developed due to their biological activity and their applications as O,O-donor ligands for
metal complexation. Here, three new compounds with general formula C6H11C(O)NHP(O)R2, with
R=Cl (1), C6H5NH (2) and 4-MeOC6H4NH (3) were prepared and characterized by IR, 1H, 13C and 31P
NMR spectroscopy and elemental analysis. C6H11C(O)NHP(O)Cl2 was prepared by the reaction of PCl5
and cyclohexane carboxamide in CCl4 and treating with formic acid. Compounds 2 and 3 were
synthesized by the reaction of 1 with corresponding amine in a 1:4 molar ratio. IR spectrum of 1
exhibits the characteristic band of carbonyl group (C=O) in 1719 cm–1. This band is shifted to lower
frequencies in the IR spectra of 2 and 3, (1660 and 1663 cm–1 respectively). In compounds 2 and 3,
as we observed earlier for phosphoramidate analogues, the P–Namine stretching vibrations appear at
higher frequencies than the P–Namide vibrations. The 31P NMR chemical shifts are observed at about
9.30, 9.40 and 9.32 ppm for 1-3 respectively. In 1H NMR spectra of 1 and 3, a broad peak is
observed for the proton of NHamidic at δ= 9.37 and 8.46 cm-1 respectively, but for 2 a doublet signal
(2JPNH = 6.4 Hz) was obtained for this proton.
Keywords: Carbacylamidophosphate, NMR, Chemical shift, IR spectra
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P-15
Biological Active Cyclometallated Organoplatinum(II) Complexes Containing NAromatic Ligands
S. Abedanzadeh* and Ahmad R. Esmaeilbeig
Department of Chemistry, University of Shiraz, Shiraz, Iran
Cyclometallated complexes are more interested for several reasons including their photochemical
and photophysical properties, their potential use as molecular devices, polymerization processes,
and more generally as products or intermediates in catalytic reactions. Significant research efforts
are currently focused on the study of cycloplatinated complexes due to their potential antitumoural
activity. The design of platinum-based antitumour agents constitutes an indispensable part of the
development of anticancer drugs. Platinum species have potential medicinal applications due to
their cytotoxicity. Platinum drugs have an enormous impact on the clinical cancer chemotherapy in
that they have been widely used against various solid tumours including genitourinary, colorectal,
and non-small cell lung cancers. But organoplatinum complexes as anticancer drugs are rare. In this
work, the precursor cyclometallated organoplatinum(ΙΙ) complex [Pt(CN)Cl(dmso)], CN=2phenylpyridinyl was synthesized and react with some N-aromatic ligands such as imidazole, 1methylimidazole, pyridine, 4-methylpyridine, 4,4'-bipyridine. All complexes are characterized by
multinuclear (1H, 13C) NMR spectroscopy, IR and microanalysis. Cytotoxic properties of all of them
are under study.
Keywords: Cyclometallated Complexes, Organoplatinum, Anticancer drug, N-aromatic ligands,
Cytotoxicity
P-16
Sonochemical Syntheses of a New Nano-plate Lead(II) Coordination Polymer
Constructed of Maleic Acid
L. Aboutorabi, A. Morsali*, P. Hosseinpour
Department of Chemistry, Payame Noor University, Abhar, Zanjan, Iran
A coordination polymer contains metal ions linked by coordinated ligands into an infinite array. This
infinite net must be defined by coordination bonds and thus molecular species linked only by
hydrogen bonding. These compounds orient in different directions and form 1D, 2D and 3D nets.
Nanometer-sized structures of metal coordination polymers are attractive to research, since their
unique properties are controlled by the large number of surface molecules and Several different
synthetic approaches have been offered for the preparation of nanomaterials. Sonochemistry is the
research area in which molecules undergo a chemical reaction due to the application of powerful
ultrasound radiation (20 kHz to 10 MHz). In this paper we have described a simple synthetic
sonochemical preparation of a new nano-structured lead(II) coordination polymer with maleic acid
(H2Mal), [Pb(µ7-Mal)]n (1), that has been characterized by scanning electron microscopy, X-ray
powder diffraction, elemental analysis and IR spectroscopy. The compound 1 was structurally
characterized by single-crystal X-ray diffraction too. Thermal stability of nano and bulk samples of
compound 1 were studied and compared each other. After calcination of nano-sized compound 1 at
600 °C, pure phase mico-sized lead(II) oxide has been produced. The crystal structure of
compound 1 consists of a two-dimensional polymer and shows that the coordination number of Pb2+
ions is seven. This Nano-sized coordination polymer has several applications due to their catalysis,
nonlinear optics, gas separation, magnetic properties, and molecular recognition.
Keywords: Nano-plate, Lead(II) oxide; Maleic Acid; Crystal structure
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P-17
Spectroscopy and equilibrium study of the complexes formation of salen type Schiff
base ligands with dimethyletin(IV)dicholoride in chloroform
Islam abroshan and Ali Hossein Kianfar*
Department of Chemistry, University of Yasouj, Yasouj, Iran
Salen type of Schiff bases have been used as ligands can coordinate to transition and main group
metals. Several investigations have been done on the synthesis and molecular structure of tin Salen
Schiff base complexes. These compounds were synthesized in specific conditions. Investigations
show that, the organotin(IV) halides are in equilibrium with the porphyrins. The metal Schiff base
complexes react with organotin(IV) halides in an equilibrium condition. In the other hands, there is
a little evidence about equilibrium reactions between organotin(IV) halides with salen Schiff base
ligand. The present study describes the complex formation of dimethyeltin(IV)dicholoride with
salen(N, N,, -bis(salycilaldehyde)ethylenediimine) type N2O2 Schiff base ligands have been as a
neutral tetradentate ligands through its O or N atoms. The formation constants were measured
using UV-Vis spectrophotometric titration far 1:1 complex formation and by making use of ketelaar
equation in the range of 15-30º C. Thermodynamic parameters were determined by making use of
von ,t Hoff equation. The formation constant of the Schiff bases with dimethyletin(IV)dicholoride in
chloroform decreases according to the following trend: 3-MeOSalen > 4-MeOSalen > 5-MeOSalen
Salen > 5-BrSalen, and
Me2Salen > Salpn > Salen > Salophen
Keywords: Schiff Base, Dimethyletin Dichloride, Formation Constant, Complex Formation
P-18
A New Manganese (III) Schiff Base Complex as a Mild and Efficient Catalyst for
Oxidation of Benzylic Alcohols
A. Adabi Ardakania*a, H. Kargarb, R. Kiac
Islamic Azad University-Ardakan Branch, Yazd, Iran
Department of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran.
c
Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran.
a
b
The oxidation of alcohols to carbonyl compounds is one of the most important and fundamental
reactions in synthetic organic chemistry. Transition metal salen complexes recognized as powerful
homogeneous catalysts in the oxidation reactions by various single oxygen atom donors such as
NaClO, PhIO, KHSO5, H2O2, and NaIO4. A number of methods are known for alcohol oxidation, until
recently the traditional oxidation reactions have been performed with classic reagents such as
persulfate and dichromate salts. These reagents are moderately expensive, toxic, corrosive,
instable, no selectivity and dangerous procedure for preparation, over oxidation to carboxylic acids
and moisture- sensitive oxidants. In this wok, we report the oxidation of benzylic alcohols with nBu4NIO4 in the presence of imidazole as axial ligand. In comparison with the data reported in the
oxidation of benzylic alcohols by various reagents, our system shows the following advantages: (i)
mild reaction conditions; (ii) high yields; (iii) short reaction times.
Keywords: Manganese (III) complex, Schiff base, Oxidation, Benzylic alcohols.
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P-19
Synthesis, characterization and biological studies of Co(II), Ni(II), Cu(II) and Cd(II)
complexes with5-(2-pyridyl)-2-(3,5-dinitro benzene)1,3,4- oxadiazole on McCoy cell
A. Adeli Ardebili*,a, A. Bezaatpourb, Y. Mansoori b, S. Zahri b, M.H. Nasir Tabrizia
a: Department of Chemistry, Faculty of Basic Science,Isamic Azad University of Ardabil, Iran
b: Department of Chemistry, Faculty of Basic Science, University of Mohaghegh Ardabili 179,
Ardabil, Iran
*Email: [email protected]
Supramolecular chemistry is based on the notion of creating novel structural and functional
extended system using noncovalent interactions between prefabricated molecular or ionic building
blocks. In recent years, the design and self-assembly of architectures of supramolecular
coordination compounds have attracted great attention and increasingly become a major research
area for their potential applications in separation, selective inclusion, ion exchange, molecular
recognition, catalysis, magnetism, and nonlinear optical properties. Generally, there are two most
common methods for the syntheses of the supramolecular complexes within crystalline solids: selfassembly through the coordination of metal cation with polydentate ligand and self-assembly of
complementary H-bond donors and acceptors. The new complexes with the formula [Co(L)2Cl2] (1),
[Ni(L)2Cl2] (2), [Cu(L)(NO3)2] ((3) and [Cd(L)Cl2] (4), where L=(C13H7N5O5) = 5-(2-pyridyl)-2(3,5dinitro benzene)-1,3,4 oxadiazole, was synthesis and characterized by IR spectroscopy,
electronic spectroscopy, 1HNMR, atomic absorption spectroscopy (AAS) and elemental analysis. In
these complexes the oxadiazole bidentate ligand link to metal ion through the Npyridine and one of the
Noxadiazole atoms. The Cobalt (II) and Nickel (II) ions are coordination to both bidentate oxadiazole
ligand in the equatorial plane, with the tow Chlor atoms placed in the axial positions. The Cupper
(II) and Nickel (II) ions are coordinated to bidentate oxadiazole ligand with 1:1 stochiometry of
M/ligand. The biological activity of complexes was studied on McCoy cell line. The biological data of
antioxidant activity by these complexes on McCoy cells imply that the Co, Ni, Co and Cd complexes
inhibit the McCoy viability. Morphological studies showed significant change of treated cell shape
Keywords: Co(II) complex, Ni(II) complex, oxadiazole, Biological studies, McCoy cell
P-20
Synthesis, Characterization, Crystal Structure and Reactivity of a Tetradentate N2O2
Schiff base Ligand Towards Some First Row Transition Metals
a
F. Heshmatpour*,a, S. Rayatia,and M. Afghan hajiabbasa
Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran
In the last decade Schiff base ligands have received more attention, mainly because of their
extensive application in the field of synthesis and catalysis. This attention is still growing, a
considerable research effort is devoted to the synthesis of modified and supported reagents for
catalysis and materials chemistry. Another attractive feature of Schiff base ligands is that they may
be tuned both sterically and electronically by the variation of corresponding amine and aldehyde
ligand precursors. In the present work, a N2O2 Schiff base ligand derived from 2,2′dimethylpropandiamine and 2-hydroxypropiophenone has been synthesized and characterized and
its reactivity towards some transition metals such as oxovanadium(IV), copper(II), nickel(II) has
been investigated.
Keywords: Schiff base, Ligand, Crystal structure, Transition metals.
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P-21
Investigation of homogenous and heterogeneous photocatalytic activity of H3PMo12O40
a
M. Afsharia,*, s. farhadib
Department of Chemistry, University of Islamic Azad University, Shoushtar branch, Iran
b
Department of Chemistry, University of lorestan, khoramabad, Iran
Photosensitivity of polyoxometalate(POMs) in the presense of organic compounds has been well
known. Illumination of POMs at the O-M CT bands with UV-Vis light generatestrongly oxidizing
excited state. This photoexcitation of POM in the presence of organic compounds leads to the
multielectron reduction of the former without decomposition and concomitant oxidation of latter.
The corresponding reduced POM is usually reoxidized by an electron acceptor such as dioxygen and
returned to initial form that can be photoexited again. In this work, the polyoxometalate, PMo12O403, was prepared and supported on SiO2 by sol-gel technique, involving the hydrolysis and
condensation of Si(OEt)4. Herein, pure POM and SiO2-supported POM have been used as
photocatalyst for oxidation of series of primary and secondary benzylic alcohols by dioxygen in
CH3CN. The result indicated that these alcohols converted to corresponding carbonyl compounds
selectively without overoxidation. We found that POM/SiO2, as a heterogeneous system, are much
more reactive than pure POM, as a homogeneous system. The significantly higher activity of
POM/SiO2 are attributed to increasing in the specific surface area of these compounds by supporting
on SiO2. We In general, we present a green, selective and efficient phoyocatalytic method which
can aerobically oxidized a variety of alcohols to their corresponding aldehydes and ketones.
Keywords: Photocatalyst, Polyoxometalate, Heterogeneous, Homogeneous
P-22
Effects of Tectonic Changes on Supramolecular Synthons in Mercuric (II) Complexes
Containing Carboxamide Ligand
A. Aghabali, M. Mehdizadeh, M. Azizpoor Fard and H. R. Khavasi*
"making a crystal with a purpose" intimates; recognition the strategy of molecular tectonics,
probable synthons, helps the crystal engineers to design structures of unmade crystalline materials
and expansion of theoretical and experimental objects lead the designer's suppositions to the
conclusive structures. However, prediction of crystal structure's details and their consistent is still
difficult, as the little change in tecton may eliminate or produce some expected synthons, and
certainly transformation in packing, orientation of molecular building blocks and definitely most of
the crystallographic parameters will be seen. In this project we try to survey predictable π-π
stacking and other extant interaction in inorganic coordination complexes which have been made by
N-(2-ethoxy-phenyl)-2-pyrazinecarboxamide ligand and mercury (II) halides. Also we try to
compare the structures with similar compounds which has been made previously. Obviously
replacing the ethoxy group with methoxy on aromatic ring in amide segment of complex causes
significant changes in crystal packing.
Key words: Crystal engineering, Mercury, Synthon, Tectonic Changes,
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P-23
Hydrothermal Synthesis of A New Self-assembly Zinc (II) Metal Organic Framework
with nano-sized channels Based On Paddle-wheel Units
Shokufeh Aghabeygia*, Ali Mosali b
Department of chemistry, Islamic Azad University, East Tehran Branch, Qiamdasht, Tehran, Iran
b
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155-4838,
Tehran, Iran
[email protected]
a
A new Zn(II) metal organic framework with nano-sized channels from 4,4΄-bipyridine (4,4΄-bipy)
and 4΄-sulfo-biphenyl-4-carboxylate (sbpc2-) ligands, {[Zn(µ-4,4΄-bipy)1.5(µ-sbpc)]·5H2O}n (1), has
been synthesized by hydrothermal method. Compound 1 was characterized by X-ray powder
diffraction, IR spectroscopy and elemental analyses as well as studied by single-crystal X-ray
crystallography. The structural studies show the Zn atoms have six–coordinate geometry with a
distorted octahedral environment constructed with paddle-wheel [Zn2(OOC)4] building units with
4,4΄-bipy and sbpc2- linkers stacked over each other to generate three-dimensional nano-sized
channels occupied by guest H2O molecules. Self-assembly of this compound in the solid state is
likely caused by coordination bonds and hydrogen bodings. Powder X-ray diffraction study indicates
that the compound 1 is single crystalline phase and that this phase is identical to that obtained by
single crystal diffraction.
Keywords: Crystal structure; Thermal properties; Nano-matterials.
P-24
ُSynthesis and characterization of Nanocomposite ZnO on SiO2 glass by sol-gel
method
Mirabdolah S. Sadjadi 1, Shokufeh Aghabeygi2*. Nazanin Farhadyar1
Department of Chemistry, Sciences and Research Campus, Islamic Azad University,
Tehran, Iran
2
Department of Chemistry, , Islamic Azad University, East Tehran branch, Qiamdasht
,Tehran,Iran
[email protected]
1
The nano-ZnO embedded SiO2 glass was prepared by sol-gel method. During this study, zinc
oxalate was prepared in aqueous using zinc acetate and oxalic acid as precursors. The thermogravimetric analysis (TGA) was showed formation of ZnO at 400 °C. Nano-size zinc oxide was
obtained by thermal decomposition of aqueous mediated zinc oxalate at 450 °C. The phase purity
was confirmed by x-ray diffraction (XRD). Crystal size was determined from transmission electron
microscopy (TEM) was found to be 15–25 nm for the aqueous mediated ZnO. Scanning electron
microscope (SEM) also revealed different nature of surfaces and microstructures for zinc oxide
obtained in aqueous.
Keywords: ZnO, Nanocomposite , SiO2 glass , sol-gel.
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P-25
Theoretical Study of Hole Reorganization Energy in [5,5] Armchair Single-Walled
Carbon Nanotubes
Adeleh Aghagolnezhad-Gerdroudbari , Avat (Arman) Taherpour*, and Saeid Rafiei
Chemistry Department, Faculty of Science, Islamic Azad University Arak Branch,,
P. O. Box 38135-567, Arak, Iran
[email protected]
[email protected]
The reorganization energy is the energy it would take to force the reactants to have the same
nuclear configuration as the products without permitting the electron transfer. Electron transfer
(ET) is one of the most important chemical processes in nature, playing plays a central role in many
biological, physical and chemical (both organic and inorganic) systems. Solid state electronics
depends on the control of the ET in semiconductors, and the new area of molecular electronics
depends critically on the understanding and the control of the transfer of electrons in and between
molecules and nanostructures. Nanotubes are cylindrical fullerenes that can be either single-walled
(SWCNT) or multi-walled; the former attract more attention due to their unique electronic, optical
and spectroscopic properties. One of the most recognizable types of carbon nanotubes is the (5,5)
armchair single-walled carbon nanotube. The number of carbon atoms (n) of the SWCNTs is
considered as one of the useful numerical and structural properties. In this study, the relationships
between this index and hole reorganization energy (λh) in [5,5] armchair single-walled carbon
nanotubes were presented and investigated.
Keywords: Carbon nanotube; Electron reorganization energy; Electron transfer.
P-26
Synthesis and Characterization of the Cu(II) complex with a oxadiazole ligand
M. Ahadia,*, S. Ghamamayb, A. Nori majda , I. Sadraeec
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Ardabil, Iran
b
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Ghazvin ,
Iran
c
Department of Chemistry, Faculty of Science, Islamic Azad University, Saveh Branch, Savehl, Iran
a
1,3,4-oxadiazole derivatives, are biologically important molecules. The oxadiazole molecules act as
spacer via coordination,hydrogen bonding and show intermolecular cooperative interaction.
Oxadiazole derivatives, which belong to an important group of heterocyclic compounds, have been
the subject of extensive study in the recent past. Numerous reports have highlighted their
chemistry and uses. Oxadiazole derivatives show diverse biological activities, such as antituberculostatic, antiinflamatory,analgesic, antipyretic and anticonvulsant. 1,3,4-oxadiazole-2-thiones
are biologically active compounds; information about their 3-dimensional structures may be of great
interest for rational drug design. 1,3,4-oxadiazole-2-thione consists of an equilibrium mixture of its
thione and thiol forms, therefore it will be of interest to investigate the bonding mode of oxadiazole
in their complexes. In this research we report preparation of a new complexese of copper (II) with
the ligand of 5-pyridyl-1,3,4 oxadiazole-2-thiol. The ligand and complexes are characterized by FTIR, UV-Vis, 1H-NMR, 13CNMR spectroscopy.
Keywords: Oxadiazole Complexes; Copper (II) Complexes; Acid hydrazide; Carbon disulfide.
46
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P-27
Controlled synthesis of highly ordered LaFeO3 nanoparticle using a ultrasonic route
a
A. Ahanin-Jana, M. Khorasani-Motlagha,*, M. Noroozifara
Department of chemistry, University of Sistan & Baluchestan, Zahedan, Iran
Metal oxides and perovskite are being employed as catalysts for various applications. LaFeo3 is one
of the important perovskite widely reported for various applications including solid oxide fuel cells,
oxygen permeation membranes, as environmental catalyst, etc. Such materials have also been
found to be suitable components as electrods in high temperature environments. The solids are also
catalytically active for hydrocarbons oxidation and for combustion and can be used in sensors and
solid electrolytes. In this paper, we report a simple method to prepare LaFeO3 nanocrystal. In this
chemical synthesis method, pure phase formation can be accelerated, as it involves mixing of La
and Fe chloride with 1:1 molar ratio with using different surfactants. Then the mixture was
transferred into an ultrasonic, and stirred for 1 h at 60 °C. The resulting products were centrifuged
for 15 min at 3000 rpm, and pure perovskite crystal phases were achieved at final calcinations
temperature of 800 °C. The final samples were then confirmed by different techniques. The
morphology and particle sizes of the prepared samples were determined by FT-IR, XRD, SEM and
EDX and results clearly show that the orthorhombic perovskite structure.
Keywords: LaFeO3, Perovskite, Ultrasonic, SEM, FT-IR, XRD.
P-28
Synthesis, measurement of structural and magnetic properties of LaFeO3 nanorods
a
A. Ahanin-Jana, M. Khorasani-Motlagha,*, M. Noroozifara
Perovskite-type oxides display prominent catalytic activities in many fields such as the total
oxidation of methane and of volatile organic compound. Perovskite oxides have general formula
ABO3, where the 12-coordinated A sites may be occupied by rare-earth, alkali or other large ions
and the 6-coordineted B sites are usually filled with transition metal cations. In the paper
perovskite-type LaFeO3 nanoparticles were synthesized by co-precipitation method from La and Fe
chlorides with 1:1 molar ratio with using different surfactants. The precipitation after reflux was
dried in oven and the resulting powder was calcinated at 800 °C. The resulting nanoparticles
characterized by means of x-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), Scanning electron microscopy (SEM). Also the magnetic properties were defined by VSM. SEM
images indicated that the particles were short homogenate nanorods (77×335 nm). The FT-IR
spectrum of LaFeo3 shows absorption band at 558 cm-1 attributed to Fe-O stretching vibration and a
band around 430 cm-1 may be attributed to O-Fe-O deformation vibration. LaFeo3 perovskite with
orthorhombic structure were obtained, with Co-precipitation that is a suitable method for the
control of nanoparticle sizes with variation of the reaction conditions. The results were showed that
calcinatuon temperature, pH, kind of surfactant and conditions of reaction affect particle size,
morphology and specific surface.
Keywords: LaFeO3, Perovskite, Co-precipitation, XRD, SEM, FT-IR
IICC12
47
P-29
Synthesis and coordination chemistry of new tetradentate N2S2 donor Schiff-base ligand
PBBD and synthesis of new dinuclear copper(І) complexes
a
k. Marjania, E. Ahmadia,*, M. Mousavib
Faculty of Chemistry, Tarbiat Moalem University, Tehran, Iran
b
Islamic Azad University, Saveh branch, Saveh, Iran
Schiff-bases are condensation products of primary amines with carbonyl compounds with a general
formula RHC=N-R′. They have had significant importance in development of coordination
chemistry; because, Schiff bases are potentially capable of forming stable complexes with metal
ions. There has been a growing interest in recent years toward the crystal structures and properties
of copper (І) complexes with multidentate Ligands, particularly in view of their potential applications
in metallosupramolecular assemblies and bioinorganic chemistry. With flexible ligands, the
competition between bridging and chelating coordination modes is an important factor in producing
mono, di, and polynuclear metal complexes. We herein report the synthesis and structure of new
copper(І) complexes [Cu2(µ-І)2(PBBD)] in which the tetradentate Schiffbase ligand (PBBD) acts as a
bis-chelating ligand bridging between two copper(І) centers. The tetradentate Schiff-base ligand
PBBD was prepared under mild conditions. [Cu2(µ-І)2(PBBD)] was prepared by the reaction of CuI
and PBBD in 2:1 molar ratio in acetonitrile. These compounds have been characterized by elemental
analyses CHN, FT-IR, UV–Vis and 1H NMR spectroscopy.
Keywords: Schiff bases, N2S2 -bis-chelating ligand, transition metal, Copper(І) complexes.
P-30
Synthasis and characterizaton and crystal structural determination of new nickel(II)
macroacyclic complex
a
M. Ahmadia , H. Keypoura,* and A. A. Dehghani-Firouzabadib
b
Department of Chemistry, University of Yazd, Yazd, Iran
The study of polyamine complexes has contributed in large measure to the rationalization of
coordination compound formation. The basic nitrogens centers in the structure of the polyamines
enable them to act as potential sites for binding metal ions. In this work, first we prepared new
pentadentate amine(N5), N1-(2-aminoethyl)-N1,N3-bis(2-pyridinemethyl) propane-1,3-diamine. After
the new macroacyclic complex were prepared by tamplate [1+1] condensation of pentadentate
amine (N5), N1-(2-aminoethyl)-N1,N3-bis(2-pyridinemethyl)propane-1,3-diamine and Ni(ClO4)2.6H20.
The pentadentate amine characterized by IR , 1H and 13C NMR. Then the macroacyclic complex
characterized by IR , mass spectroscopy and X-ray diffraction. The IR spectram of the complex
shows absorption bonds at 3273 and 3331 cm-1 corresponding to an (NH2) bond and 2281
corresponding to an Acetonitrile molecule. The crystal structure of the asymmetrical
[Ni(CH3CN)L](ClO4)2 complex was determined by X-ray diffraction. It is shown that in the solid state
the complex adopts a distorted octahedral geometry.
Keywords: Macroacyclic complex, Nickel complex, Pentadentate amine, Crystal structure.
48
IICC12
P-31
Synthesis and characterizaton of new zinc(II) and cadmium(II) macrocyclic Schiff base
complexes derived from condensation of 4,9-bis(2-methylpyridine)-4,9-diazadodecane1,12-diamine and 2,6-diformyle-4-methylphenol
a
M. Ahmadia, H. Keypoura,* and R. Golbedaghib
Faculty of Chemistry, Bu-Ali Sina University. Hamedan, 65174, Iran
b
Department of Chemistry, University of Payame Noor, Iran
Macrocyclic Schiff base complexes have attracted much attention since the early 1980s, and several
reviews covering this area of research have appeared. Template Schiff-base condensations between
dicarbonyl compounds and diamines are among the simplest and most popular methods for
macrocycle synthesis. The size and preferred coordinaton geometry of the metal ion control the
structure of the condensation products. In the present work, first we prepared new branched
hexadentate amine (N6),4,9-bis(2-methylpyridine)-4,9-diaza dodecane-1,12-diamine. After two new
Schiff base macrocyclic complexs were prepared by tamplate [1+1] cyclocondensation of 2,6diformyle-4-methylphenol and the branched hexadentate amine in the presence of Zn(II) and
Cd(II) metal ion in methanol. The branched hexadentate amine characterized by IR, 1H and 13C
NMR. Then the Schiff base macracyclic complexes characterized by IR and mass spectroscopy. The
IR spectra of the complexes show intense absorption bonds at 1656 ([ZnL]2+) and 1654([CdL]2+)
cm-1, corresponding to an imine bond and no peaks assignable to unreacted amine or carbonyl
groups.
Keywords: Schiff base, Haxadentate amine, Macracyclic complexes, Zinc(II) complexs,
Cadmium(II) complex
P-32
Synthesis and characterization of two novel manganese(II) macroacyclic Schiff base
complexes derived from condensation new pentadentate amine (N5) and 2pyridinecarboxaldehyde or 2-pyrrolecarboxaldehyde
a
M. Ahmadia , H. Keypoura,* and R. Golbedaghib
Faculty of Chemistry, Bu-Ali Sina University. Hamedan, 65174, Iran
b
Department of Chemistry, University of Payame Noor(PNU), Iran
Schiff base complexes are considered to be among the most important stereochemical models in
main group and transition metal coordination chemistry due to their preparative accessibility and
structural variety. They have played a key role in the development of coordination chemistry.
Resulting in an enormous number of publications.ranging from pure synthetic work to modem
physicochemical and biochemically relevant studies of metal complexes. In the present work, first
we prepared new pentadentate amine(N5), N1-(2-aminoethyl)-N1,N3-bis(2-pyridinemethyl) propane1,3-diamine. Then the macroacyclic complexes has been synthasis by condensation of 2pyridinecarboxaldehyde or 2-pyrrolecarboxaldehyde with the pentadentate amine N1-(2aminoethyl)-N1,N3-bis(2-pyridinemethyl)propane-1,3-diamine in the presence of Mn(II) metal ion.
The pentadentate amine characterized by IR, 1H and 13C NMR. Then the Schiff base macroacyclic
complexes characterized by IR and mass spectroscopy. The IR spectra of the complexes show
intense absorption bonds at 1668 ([MnL1]2+) and 1667([MnL2]2+) cm-1, corresponding to an imine
bond and no peaks assignable to unreacted carbonyl groups. The crystal structure of the
asymmetrical, [MnL1](ClO4)2 complex was determined by X-ray diffraction. It is shown that in the
solid state the complex adopts a distorted octahedral geometry.
Keywords: Schiff base, Pentadentate amine, Macroacyclic, Mn(II) complex, Crystal structure.
IICC12
49
P-33
A Theoretical Study of Stability, Comparing Between Two Nitrogen Derivatives of
Fullerene (C60)
R. Ahmadi*, K. kalateh, D. Torabi. M
Department of Chemistry, Share-Rey Branch, Azad University, Tehran, Iran
Since the discovery and the bulk production of fullerenes an integrated research field involving
organic transformations of these all-carbon hollow-cluster materials has emerged. C60 has been the
most thoroughly studied member of fullerenes because it (1) is produced abundantly in the carbon
soot by the arc discharge of graphite electrodes, (2) has high symmetry (icosahedral (Ih) with all 60
carbons chemically equivalent), (3) is less expensive, (4) is relatively inert under mild conditions,
and (5) shows negligible toxicity. In this study in order to determine the optimized geometries,
energies، dipole moment، atomic charge and other properties of (C60-C4H10N2) and (C60-C4H11N2) we
have performed quantum chemical ab initio calculations in HF/6-31G* method، in gas phase. The
results show that dipole moment، energies of HOMO and LUMO levels neutral case (C60-C4H10N2)
are more than ionic case (C60-C4H11N2). Also the length of N-C and N-H bonds terminal of molecules
in neutral case is longer than ionic case. So (C60-C4H11N2) is more stable than (C60-C4H10N2).
Keywords: Fullerene (C60), Ab Initio, Cluster Materials, HF
P-34
Dependence of (Valence/Charge) Ratio to Stability of Complex [Co(C6H6N4)2(H2O)2]Cl2
with Different Halogen Substitutions by Hartree Fock Method
R. Ahmadi*, S. Poush Nejad, F. Rahbar yaghoubi
In this study [Co (C6H6N4)2(H2O)2] Cl2 Complex has been evaluated . There are independent cation
and two chloride Anions in the crystal structure of this Compound , the Co(II) cation is coordinated
by four Nitrogen(N) atoms from two biimidazole and two oxygen(O) atoms of two water molecules;
Cobalt (Co) atom is at a position of site symmetry 2/m . In this research dependence of
(Valence/Charge) ratio to stability of organometalic complex[Co (C6H6N4)2(H2O)2] Cl2 with changing
Halogen atoms in the position of H39 has been interested. All calculation have performed in HF/631G* method and gas phase. The results show that with decreasing electro negativity from F to Br
the (Valence/Charge) ratio for (C17, C36 & C38) atoms and stability of complex increase.
Keywords: HF, (Valence/Charge) Ratio, Stability, Gas phase
50
IICC12
P-35
Ab Initio Quantum Chemical Studies of 13C-NMR Shielding Tensor [Cu
(C2H2ClO2)2(C12H8N2)(H2O)] Complexes with Different Halogen substitutions
R. Ahmadi*, M. Khosh Tarkib, S. Khalilian
In this study [Cu(C2H2ClO2)2(C12H8N2)(H2O)]Complex have been evaluated .In this complex the
Cu(II) ion is five coordinated by two Nitrogen (N) atoms from the (1,10-phenanthroline) ligand,
two Oxygen (O) atoms from two (2-chloroacetate) ligands and one water molecule , in a distorted
square-pyramidal geometry. In this research the different halogens substitutions effects (in the
position of H40) on the NMR shielding tensors in organometalic complex [Cu
(C2H2ClO2)2(C12H8N2)(H2O)] have been investigated with quantum mechanical calculations. All
calculations have been done in gas phase with ab initio method at HF/6-31G*.These results show
that for ( C28, C30 ,C31 and C32) in the mentioned Complex, the shielding tensors (σ11 , σ22 , σ33 ) with
decreasing electro negativity from (F) to (Br) increase
Keywords: 13C-NMR, Shielding Tensors, HF, Organometalic.
P-36
The Comparison of Participation Amount of p-Atomic Orbital with Changing Halogen
Substitutions in Organometalic Complex [Cu (C6H5O3) Cl (C12H8N2)] with Ab Initio
Calculations
R. Ahmadi*, F. Rahbar yaghoubi, S. Poush Nejad,
In this report Organometalic Complex [Cu (C6H5O3)Cl(C12H8N2)], has been studied. The two
coordinating atoms of the two heterocyclic ligands comprise the square plane, and the chlorine
atom occupies the apical position of the coordination environment. In this research, the effect of
various halogens substitutions (F, Cl, Br) on the participation amount of p-atomic orbital in σ bonds
around the position of C22 in [Cu (C6H5O3)Cl(C12H8N2)] complex have been calculated in gas phase
by using HF/6-31G* method, and the NBO as implemented in Gaussian 98. The results indicate that
with decreasing electro negativity substitution from F to Br, the stability and amount of participation
of p-atomic orbital in (C23-C24) and (C23-C25) bonds increase.
Keywords: σ Bonds, Participation, NBO, Stability, Halogens Substitutions
IICC12
51
P-37
synthesis, characterization and structural analyses of diamine-bridged bimetallic
complex
R. R. Khojasteh*, M. Ahmadzadeh, S. Lotfalian saremi
Department of chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran
In recent years, There has been extensive interest in diamine-bridged bimetallic complexes for their
structural diversity and potential applications in the fields of catalysis, electrical, conductivity,
magnetism and photochemistry. New homobimetallic complex of molybdenum (VI) [(MoO2L)2 (µ-NN)] (L=2,2′-bipyridine and µ-N-N=1,4-phenylenediamine) obtained of reaction MoO2 (acac)2
{acac=acetylacetonato) with 2,2′-bipyridine and 1,4-phenylenediamine ligands, and characterized
by spectral techniques such as elemental analysis, IR, NMR spectroscopy.
Keywords: Mo-Mo bimetallic; p-phenylenediamine; bipyridine
P-38
Investigation Catalytic Activity of Polyoxometalate Contains Cerium Heteroatom in
the Synthesis of Dihydropyrimidinones.
M. Ajoodanian, V. Mirkhani*, A. R. Khosropoor, I. Mohammadpoor-Baltork, S. Tangestaninejad, M.
Moghadam
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
E mail. mirkhani @sci.ui.ac.ir
Polyoxometalates are a group of metal-oxygen clusters, which gain various applications in many
fields because of their outstanding properties such as size, mass, electron transfer and Bronsted
acidity. Metals that commonly used in these compounds are W, Mo, V, which are in their highest
oxidation state (d0 & d1). Due to the lack of electron in the d orbitals of these metals, they can
accept electron and be as acidic and oxidative catalysts. 3,4-Dihydropyrimidine-2-(1H)-ones
(DHPMs) and their derivatives are pharmacologically important compounds because of different
biological activities, including antiviral, antibacterial and antitumor. General route for synthesis of
DHPM is one-pot cyclocondensation of aldehyde, β-ketoester and urea. However, some of the
reported methods for the preparation of these heterocycles suffer from disadvantages such as long
reaction times, low yields and tedious work-up. Therefore, introducing a new mild procedure for the
synthesis of these compounds are of practical importance. In this work, a series of
dihydropyrimidinones have been synthesized by one-pot reaction of aldehyde, β-ketoester and urea
in the presence of (NH4)8[CeW10O36]·20H2O under solvent-free conditions. Under this conditions, the
corresponding DHPMs were obtained in good to excellent yields. The catalyst was reused several
times.
Keywords: Polyoxometalate, Biginelli reaction, Dihydropyrimidinones, One-pot, Synthesis, Solventfree.
52
IICC12
P-39
Preparation and Characterization of Lead(II) Oxide Nano-structures
a
Shabnam Sheshmani a,*, M. Ranjbar b, S. Heydar Mahmodi Najafi b, Neda Akbari Mobarakeh a
Department of Chemistry, Islamic Azad University, Shahr-e Rey Branch, P. O. Box 181155-144,
Tehran, Iran
b
Department of Chemical Industry, Iranian Research Organization for Science and Technology
P. O. Box 15815-3538, Tehran, Iran
Sonochemical preparation of a nano-rod compound from the reaction between minoxidil ligand,
(2,4-diamino-6-piperidine-1-yl)pyrimidine N-oxide, with a mixture of lead(II) acetate and potassium
nitrite using a heat gradient in an ultrasonic vessel was investigated. The scanning electron
microscopy (SEM) micrograph indicated that this compound consist of nanometric particles, which is
in agreement with the powder X-ray diffraction (XRD) results. To examine the stability of the nanorods, thermal gravimetric analysis (TGA) was carried out. The weight loss was due to the
decomposition of nano-rod compound to lead(II) oxide. The nano-structures of PbO were prepared
from nano-rod compound as a precursor by hydrothermal reaction and calcination in autoclave and
furnace at nitrogen atmosphere, respectively. The IR spectrum of this compound confirmed the
formation of PbO. The XRD pattern of this compound can be indexed to PbO orthorhombic lattice in
the space group Pcam with the parameters of a = 5.4903Å, b = 5.89200Å, c = 4.75200Å, Z = 4.
The SEM micrograph and energy-dispersive X-ray (EDX) analysis confirmed the production of PbO
nano-structures compound. In this study, nano-structured of lead at high yield produced in absence
of high temperature/pressure. Also, the products were good candidates for specific industrial
applications.
Keywords: Lead(II) oxide, Minoxidil, Coordination polymer, Sonochemical, Nano-structures
P-40
Synthesis and characterization and release of 5-aminosalicylic acid-intercalated Zn-Allayered double hydroxides
a,b
F.F. Akbarnejad seyed abadi a,*, S. Dr.Z.rezvanib
Department of Chemistry, Azarbaijan University of Tarbiat Moallem, Tabriz, Iran
Layered double hydroxides (LDHs),or so-called anionic clays ,consist of cationic brucite-like layers
and exchangeable interlayer anions. The 5-aminosalicylic acid anions (5-ASA-) intercalated Zn-Al
layered double hydroxides (LDHs) with variable Zn/Al molar ratios have been synthesized by coprecipitation (cp) methods. The solids have been characterized using several physicochemical
techniques,i.e, powder X-ray diffraction(XRD), Fourier-transform infrared spectroscopy(FT-IR), UVvisible spectroscopy(UV-VIS), thermogravimetry and differential thermal analysis(TG-DTA),
inductively coupled plasma(ICP) emission spectroscopy, CHN elemental microanalysis and (SEM)
scanning electron microscopy. Drug release characteristics of the pillared LDH materials were
investigated by a dissolution test a simulated intestinal fluid (buffer at PH 7.8). The results show
that the drug release of supramolecular LDH materials was a slow process, suggesting that these
drug-inorganic hybrid materials can be used as an effective drug delivery system.
Keywords: Layered double hydroxides, Drug delivery System, 5-Aminosalicylic acid,
Supramolecular, Intercalation, Release
IICC12
53
P-41
Reactivity of mercury(II) halides with the unsymmetrical phosphorus ylide
Ph2PCH2CH2PPh2=C(H)C(O)CH2OC(O)CH2CH3: synthesis and spectral characterization
F. Akhlaghi Bagherjeri, S. J. Sabounchei a, A. Dadrass b and M. Hosseinzadeh
a
Faculty of chemistry, Bu–Ali Sina University, Hamedan, 65174, Iran
b
Department of chemistry, University of Urmia, Urmia, 57165, Iran
The unsymmetrical phosphorus ylide, [Ph2PCH2CH2PPh2=C(H)C(O)CH2OC(O)CH2CH3] (2) was
prepared by the treatment of triethylamine on the monophosphonium chlorid
[Ph2PCH2CH2PPh2CH2C(O)CH2OC(O)CH2CH3]Cl (1) derived from 1,2-bis(diphenylphosphino)ethane
(dppe) and ClCH2C(O)CH2OC(O)CH2CH3. The reaction of (2) with Hg(II) halides in equimolar ratios
using dry methanol as solvent to form polymeric products with the composition
HgX2[PPh2CH2CH2PPh2C(H)C(O)CH2OC(O)CH2CH3]}n, where X = Cl (3), Br (4), I (5). The complexes
have been characterized by elemental analysis, IR, 1H, 31P NMR spectra. In These complexes the
ylide exhibits a monodentate P-coordination with the dangling ylide.
Keywords: Mercury(II) halides, Phosphorus ylides, Resonance stabilization,Coordination polymer
P-42
Synthesis and characterization of new mononuclear mercury(II) complexes of a
bifunctionalized ylide containing five-membered chelate ring
F. Akhlaghi Bagherjeri, S. J. Sabouncheia, A. Dadrasb and M. Hosseinzadeh
a
b
Department of chemistry, Urmia University, Urmia, 57165, Iran
The reaction of Ph2PCH2PPh2 (dppm) with ClCH2C(O)CH2OC(O)CH2CH3 (1:1molar ratio) in
chloroform produces a new monophosphonium salt [Ph2PCH2PPh2CH2C(O)CH2OC(O)CH2CH3]Cl (1).
Further, by reacting monophosphonium salt with the appropriate base the bidentate phosphorus
ylide, [PPh2CH2PPh2
C(H)C(O)CH2OC(O)CH2CH3] (2) was obtained. The reaction of (2) with
mercury(II) halides in equimolar ratios using dry methanol as solvent yielded the P, C-chelated
complexes, {HgX2[Ph2PCH2PPh2C(H)C(O) CH2OC(O)CH2CH3} where X = Cl (3), Br (4), I (5).
Characterization of the obtained compounds was also performed by elemental analysis, IR, 1H, 31P,
and 13C NMR.
Keywords: Phosphorus ylides Resonance stabilization, Mecury(II) complexes
54
IICC12
P-43
New Chemical Solvent and Solvation Phenomena of Silicate-lime Composites
S.Ghammamy*, S.Alavi Vosoghi, Z.Shokri Aghbolagh, N.Ahmadi
Department of Chemistry, Faculty of Science Imam Khomaini International University, Qazvin, Iran
Silica-lime composites had been used many years ago in all of world specially in Iran. These kind of
materials are very hard, strong and resisted to crashing and reconstruction. In reconstruction of
ancient building it is need to destroying these composites materials. In this research after analysing
of these kind of materials some mixed chemicals usedand found a number of special solvents that
could solve these composites. These solvent used for destroying of different kinds of silica-lime
composites. The results confirmed by different scientific researches.
Keywords: silica, lime, composites, chemical, solvents
P-44
Platinum(II) complexe with bidentate iminopyridine ligand
a,b
Roghaieh Aleeshaha, Saeed Dehghanpour*b,
Department of Chemistry, Alzahra University, P.O.Box 1993891176, Tehran, Iran
email: [email protected]
The crystal structures of platinum(II) complexe, [PtCl2L] (L = (4-fluorophenyl)pyridin-2ylmethylene-amine, was determined using single crystal X-ray diffraction. The coordination
polyhedron about the platinum (II) center in the complexes is best described as a distorted square
planar. Platinum complexes with the diimine ligands have inspired considerable research efforts. For
example, such complexes have found widespread use as optical materials, DNA intercalators and
solar cell dyes. The geometry around the d8 Pt center is a distorted square plane, where the
relatively small N(1)–Pt–N(2) bond angle of 80.51(8)° is a result of chelating ligand steric
constraints. The bond angles around the Pt atom are consistent with a planar geometry, which sum
to 359.96°. The relatively short C=N bond length of 1.284(16) Å for C(6)–N(2), compared to the
C(1)–N(1) bond length of 1.329(17) Å and the C(5)–N(1) bond length of 1.369(18) Å in the pyridine
ring, is consistent with a lack of imine double-bond delocalization. A mean plane analysis of the five
atoms comprising the transition metal square plane reveals a maximum deviation from ideality of
0.095(12) Å for N(1). The aryl ring of the pyridinylimine ligand containing C(7)–C(12) is tilted outof-plane with respect to the metal chelate plane with a calculated torsion angle of 42.64(6)°
between the two planes. Terminal phenyl rings, which contain bulkier non-hydrogen substituents
tend to adopt a nearly perpendicular position relative to the metal chelation plane in structurally
related compounds. The molecules stack in the a direction in a head to tail fashion with two
different PtּּּPt distances.
Keywords: platinum(II) complexe, diimine ligands, single crystal X-ray diffraction, distorted square
planar
IICC12
55
P-45
Synthesis of Cobalt Salophen Complex and Study of Its Anticancer Activity
a
M. Alema*, B. Shaabanib
Department of Chemistry,Facutly of Science,Islamic Azad University,Ardabil Branch,Ardabil,Iran
a
Department of Chemistry,Islamic Azad University,Young Researchers Club,Ardabil
Branch,Ardabil,Iran
b
The chemistry of salophen Schiff base, driven from the condensation reaction of 1,2diaminobenzene with salicylaldehyde is an area of increasing interest. Metal complexes with these
bases have numerous applications, such as, in the treatment of cancer, as antibactericide agents,
as antivirus agents, as fungicide agents and for other biological properties. In this work we have
synthesized cobalt complexe with salophen and characterized them with IR, Uv/Vis and
conductance measurements. Cancer cells 742 treatments with these complexes via MTT showed
their anticancer activity against the colonized cancer cells. In this study we observed a reduction in
cancer cells growing near to 80%. The microscopic images that we prepared from the cells showed
that the cells were dispersed as granules concluding that they were dead. Increasing of the
concentration of complexes causes an increase in their anticancer activities.
Keywords: Cobalt, Salophen, Anticancer,742
P-46
Catalytic effect of metalloporphyrin with hydroxyphenyl ring substituted
metalloporphyrin
T. Ale-mohammad, N. Safari*
(Email: [email protected])
Cytochrome P-450 enzymes (P-450s) are a large group of heme enzymes involved in many
bioprocesses in the body and catalyze the transfer an oxygen atom from molecular oxygen into a
wide range of organic compounds. As biomimetic models, metalloporphyrins have been found to be
good catalysts for variety oxygenation reactions such as olefin epoxidation and hydrocarbon
hydroxylation. In this work epoxidation of olefins was studied in the presence of manganese
tetraphenyl porphyrin and some hydroxyl phenyl ring substituted manganese porphyrins as
catalyst, tetra-n-butylammonium Oxone (TBAO) as oxidant and tetra-n-butyl ammonium acetate
as axial ligand. Catalytic activity of these metalloporphyrins obtained in the following order T(2,3OHP)PMnOAc>TPPMnOAc>T(4-OHP)PMnOAc>T(2,4,6-OHP)PMnOAc>T(2,6-OHP)PMnOAc. Several
axial ligands such as imidazol, DMF, pyridine, 1-methyl imidazol and tetra-n-butyl ammonium
acetate were used. tetra-n-Butyl ammonium acetate was showed best effect under our reaction
condition. Reactions were performed in a solvent mixture of methanol and dichloromethane (1:5).
Addition of more amounts of alcohols reduced yield of product. Hydrogen bonding or hydrogen
transfer between axial ligands and the substitutents on the periphery of the porphyrin is discussed.
Keywords: Metalloporphyrin, Hydroxy, TBAO, Axial ligand.
56
IICC12
P-47
Formation of a new monomeric zincII based-pyrazine-2,3-dicarboxylate ionic complex
with 2-amino-4-methyl pyridine spacer
N. Alfi*, H. Eshtiagh-Hosseini, A. Mousavinezhad, and M. Mirzaei
Department of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran
In the past few years, supramolecular complexes have attracted extensive attention because they
possess potential properties in catalysis, magnetic behavior, optical material, and adsorption. A
various number of complexes containing transitional metal ions and bridging multifunctional organic
ligands with N- and O-donors have been reported. In particular, N-containing polycarboxylates such
as pyrazine- and pyridine-carboxylates are efficient building blocks in constructing novel
coordination compound. Herein, a new supramolecular coordination compound of zincII- based
pyrazine-2,3-dicarboxylic
acid
(pzdcH2)
with
2-amino-4-methyl
pyridine
(ampy),
(ampyH)[Zn(pzdc)2.2H2O].6H2O, has been reported for the first time. The title compound has been
characterized by means of elemental and thermal analyses, IR spectroscopy and single crystal X-ray
diffraction technique. In the title compound pzdcH2 acts as a bidentate ligand through oxygen atom
of carboxylate group and N atom of pyrazine aromatic ring. Different hydrogen bond causes the
title compound to form three-dimentional framework. The combinations of hydrogen-bonding and
metal-coordination motifs have created a interesting supramolecular motif
Keywords: Zinc, Pyrazine-2,3-dicarboxylic acid, 2-Amino-4-methyl pyridine, X-ray crystallography,
TGA, Supramolecular chemistry.
P-48
Construction of a new copperII supramolecular coordination compound containing O–
and N– donor ligand
N. Alfi*, H. Eshtiagh-Hosseini and M. Mirzaei
(e-mail: [email protected] )
Polycarboxylates are extremely popular as ligands in designing coordination compound with various
dimensionalities and network topologies. In this work, we report on a new coordination compound
of CuII atom which was successfully obtained applying proton transfer methodology. The reaction of
metallic salt with pyrazine-2,3-dicarboxylic acid (pzdcH2) and 2-amino-4-methyl pyridine (ampy)
afforded a new crystalline compound, namely (ampyH)[Cu(pzdc)2(H2O)2] (1). The compound 1 is a
mononuclear supramolecular compound which ampy acts as a counter ions and cationic fragment
as we expected. The title compound was characterized by elemental analysis, IR, and single crystal
X-ray diffraction. The structure of the title compound was further established by thermogravimetric
analysis which verifying our compound is quite thermal stable. The carried out potentiometric and
DFT calculations studies are in good agreement with solid states data.
Keywords: Copper, Pyrazine-2,3-dicarboxylic acid, Coordination compound, Crystal structure, TGA.
IICC12
57
P-49
Synthesis, Characterization and Crystal Structure Determination of Copper(II)
Complexes: [Cu(dm4bt)Cl2(DMSO)], [{Cu(dm4bt)(H2O)(tpht)}.H2O]n,
[Cu(dm4bt)Cl(Hipht)] and [{Cu(dm4bt)(H2O)(ipht)}4·2H2O]
Radhiya Al-Hashemia, Nasser Safaria,*, Saeid Amanib, Vahid Amania, Anita Abedic, Hamid Reza
Khavasia, and Seik Weng Ngd
a
b
Department of Chemistry, Arak University, Dr. Beheshti Ave, Arak 38156, Iran
c
Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran
d
Department of Chemistry, Malaya University, Kuala Lumpur 50603, Malaysia
Copper carboxylate with nitrogen donor ligands were found to exhibit a variety of pharmacological
activities, super oxide dismutase activities and cytogenetic effects. The bithiazole moiety, one
domain of Bleomycins(BLMs), was shown to be responsible for the binding of BLM to DNA.
Copper(II) complexes, [Cu(dm4bt)Cl2(DMSO)] (1),
[{Cu(dm4bt)(H2O)(tpht)}·H2O]n
(2),
[Cu(dm4bt)Cl(Hipht)] (3) and [{Cu(dm4bt)(H2O)(ipht)}4·2H2O] (4) (where dm4bt is 2,2´-dimethyl4,4´-bithiazole, DMSO is dimethyl sulfoxide, tpht is terephthalate, Hipht is hydrogen isophthalate
and ipht is isophthalate) have been synthesized and their crystal structures determined by X-ray
crystallography. They were characterized by IR, UV-Vis and EPR spectroscopy. Complex 2 is copper
terephthalate polymer has a cis-configuration terephthalate rings opposed to zigzag chains with
anti-configuration usually reported in the literature. Controlled deprotonation in the presence of
ethylene diamine results in self assemblies of 3 to form a tetramer complex of 4. Complex 4 has
two kinds of spatial isomers which are resolved by EPR and X-ray.
Keywords: Copper; 2,2´-Dimethyl-4,4´-bithiazole;
Isophthalic acid; Crystal structure.
Dimethyl
sulfoxide;
Terephthalic
acid;
P-50
Preparation and Analysis of Fe3O4 and Fe3O4 doped with Nd+3 and Co +2
P. Alimarda, M. Yousefib,* and R. Fazaelic
Department of Chemistry,Islamic Azad University Shahr-rey Branch, Tehran, Iran
b
Department of Chemistry,Islamic Azad University Shahr-rey Branch, Tehran, Iran
Department of Chemistry, Islamic Azad University South Tehran Branch, Tehran, Iran
a
c
Fe3O4 magnetic nanoparticles were prepared by the aqueous co-precipitation of FeCl3
andFeSO4.7H2O, CoN2O6.6H2O, Nd(NO3)3.6H2O with addition of sodium hydroxide. Fe3O4 magnetic
nanoparticles obtained were characterized systematically by means of X-Ray Diffraction (XRD),EDS,
Scanning Electron Microscope(SEM), Transmission Electron Microscope (TEM), Alternating Gradient
Force Magnetometer(AGFM).The results revealed that the magnetic nanoparticles were spherical
shaped with inverse spinel structure .The diameter for magnetic particle observed 15 nm .
Magnetic measurement revealed that the saturation magnetization of the Fe3O4 and Fe3O4 doped
with Nd+3 and Co+2 were 56.66 ,74.64 emu/g , respectively. It was found that the magnetic
response of the Fe3O4 increase when it doped with Nd+3 and Co+2.
Keywords: Superparamagnetic, Fe3O4, Magnetic nanoparticle, Magnetite, Doped Fe3O4.
58
IICC12
P-51
Synthesis of new Dinuclear Cis-platine complexes
S.Alimohammadia,b, S.hemmati*a, M.esmhosainib,
a. Tabriz university of medical sciense, drug applied research center
b. urmia university, chemistry department
Dinuclear platinum complexes are of special interest, because they are from a unique array of DNA
adducts (inter and interastrand cross links) and show high activity in vitro and invivo against tumor
cell lines resistant to cis-platin (cis-[PtCl2(NH3)2].The present work was aimed at the synthesis of
new Dinuclear Pt complexes and novel cis-platins which have moiety groups for linking to drug
delivery systems. For this purpose we have synthesized new di- and tetra-dendate amine ligands in
a multi- rout synthetic method as the following. Diethyl malonate converted to tetraethyl ethane1,1,2,2- tetracarboxylate, then tetra ester reduced to related tetrahydroxy derivative. Then, the
later hydroxyl derivative converted to tetra amine ligand via three steps including -OH - OTs N3 -NH2 . The resulting ligands were reacted with PtCl4 and PtCl2 (NH3)2 compounds for achieving
to the nuclear Pt complexes, All of new synthesized compounds (ligands and complexes) fully
characterized by spectroscopic methods. Also, complexes structure are under assigned by X-ray
(diffraction and single crystals)
Key word: Cis-platin, Tetra amine, Tetraole, Anti cancer
P-52
Structure and Reactivity of a Novel Twin µ-Oxo Bridge Vanadium Schiff base Complex
M. Alipour,a A. Rezaeifard*a, M. Jafarpour,a H. Stoeckli-Evansb
Institute of Physics, University of Neuchâtel, Rue Emile-Argand 11, 2009 Neuchâtel, Switzerland
a
b
In recent years, vanadium chemistry has attracted attention due to its interesting structural
features and biological relevance. Applications of vanadium compounds in medicine have focused
their in vitro and in vivo activity in the treatment of insulin deficiency, type 1diabetes, and insulin
tolerance, type 2 diabetes. Oxovanadium complexes have been shown to catalyzed a variety of
reactions such as the oxidation of alcohols and inorganic compounds like halides and sulfur oxides,
the epoxidation of alkenes and allyl alcohols, and the conversion of sulfides to sulfoxides and
sulfones. In this work, the synthesis and characterization of a novel µ-oxo bridge Vanadium Schiff
base complex crystallized as a twin’s structure has been described. The compound is a binuclear
complex with an O atom bridging two V atoms. The catalytic activity of this complex in different
oxidation reactions using various oxygen donors has been investigated.
Keywords: Vanadium, Schiff base, Structure, Oxidation, Oxo bridge.
IICC12
59
P-53
Cationic silica supported mono substituted Polyoxometalates as a reusable catalyst for
oxidation of sulfides with hydrogen peroxide
M. Alizadeh, B. Yadollahi*
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
E mail: [email protected]
Polyoxometalates are oxygen rich class of inorganic cluster systems exhibiting remarkable chemical
and physical properties, which have been applied to various fields such as catalysis, medicine and
materials science. Special properties of polyoxometalates such as thermal stability, solubility,
structure, topology and electronic behavior are important for their catalytic applications. Oxidation
of sulfides to sulfoxides or sulfones has been subjected for many studies. Oxidative desulfurization
methods are used to remove sulfur compounds, from gas oil or diesel fuels. Also Organosulfur
compounds are useful intermediates in organic synthesis. Some oxidizing agents that used for this
purpose including nitric acid, MnO2, hydrogen peroxide, and so on. Several types of POMs such as
H3PW12O40, H3PWMo11O40, and H3PW3Mo9O40 were evaluated as catalysts for Oxidation of sulfides. In
this work we immobilized Zn substituted keggin type polyoxometalate, namely [PW11ZnO39]5-, on
cationic silica nanoparticles and used them for oxidation of sulfides with H2O2 in CH3CN. The catalyst
has been characterized by FT-IR, BET, XRD, SEM, and TG-DTG methods. Results indicated that the
polyoxometalate structure retained after immobilization on silica nanoparticles. This hetrogeneous
catalyst has been shown high yields and reusability in oxidations of various sulfides with hydrogen
peroxide.
Key words: polyoxometalate, cationic silica, catalysis, oxidation, sulfide
P-54
Synthesis and Characterization of Phenylenediamine Substituted Tetraaza Macrocyclic
Ligands and their Ni(II) and Cu(II)Complexes
a
A. Zamanpour, M. Asadi*
Chemistry Department, College of Sciences, Shiraz University, Shiraz. Iran
[email protected]
Quinolines are very important compounds partially because of their pharmacological properties
which include wide applications in medicinal chemistry, notabe among them are antimalaria drugs,
anti-inflammatory agents, antiasthamatic, antibacterial, antihypertensive and tyrosine kinase
inhibiting agents. In addition, quinolines have because for the preparation of nano and
mesostructures with enhanced electronic and photonic properties. Many tetradentate Schiff bases
ligands are known to stabilize unusual oxidation states of the coordination metal. The field of
macrocyclic chemistry of metals is developing very rapidly because of its applications and
importance in the area of coordination chemistry. Transition metal complexes with macrocyclic
ligands are well known for their enhanced kinetic and thermodynamics stability. Schiff base
tetraazamacrocyclic ligands N-N', Di(quiniline 2-methylene}- 4-nitro-1,2 phenylenediimine
(QNO2phen), N-N', Di(quiniline 2-methylene}- 4-chloro-1,2 phenylenediimine (QClphen) and N-N',
Di(quiniline 2-methylene}- 4-methoxy-1,2 phenylenediimine (QOMephen) were synthesized by
reaction of 2-quinolinecarboxyaldehyde and 4-NO2- 4-Cl, 4-OMe 1,2-phenylenediamine. Then some
new mimixed ligands copper(II) and nickel(II) was prepared and characterized by elemental
analysis, mass, 1HNMR, IR, UV-Vis spectra.
Keywords: Quinolines, Pharmacological, Sciff base, Tetraazamacrocyclic ligands.
60
IICC12
P-55
Synthesis and characterization of PbS nanoparticles in MCM-41 nanoparticles
A. Pourahmada,*, Sh. Sohrabnezhadb, S. Alizadehc
Department of Chemistry, Islamic Azad University, Rasht Branch, Rasht, Iran
b
c
Department of Chemistry, Islamic Azad University, Ardabil Branch, Ardabil, Iran
a
The design and synthesis of materials with nanometer dimensions in the so-called mesoscopic size
range is currently the subject of intense research because their properties differ considerably from
those of the corresponding bulk materials. In particular, samples with particle sizes in the range 110 nm can exhibit novel electronic, optical, magnetic and chemical properties due to their extremely
small proportions. These particles have many technological applications, e.g., in magnetic recording
media, Ferro fluids, and catalysts. The use of an inorganic matrix as a host for nanocrystalline
particles can provide an effective way of tailoring a uniform size and controlling the homogeneous
dispersion of ultrafine clusters. We have studied a simple method for the synthesis of PbS
nanoparticles in MCM-41 nanoparticles. The growth of nanoparticles was started by ion exchange of
MCM-41 in a solution of Pb2+ ions, followed by treatment of the exchanged samples with Na2S
solution. The samples exhibit blue shifts in the absorption edges with respect to the bulk samples.
In spite of some changes which were appreciated in the MCM-41 framework, powder XRD results
reflect that the zeolite structure is essentially maintained and the average size of the nanoparticles
are 5-6 nm.
Keywords: Nanoparticles, Semiconductors, SEM, PbS.
P-56
Synthesis and Characterization of Platinum(IV) Complexes: [Pt(dpyam)Cl4].DMF and
[Pt(4,4'-dtbipy)Cl4]
Vahid Amania, Anita Abedib and Nasser Safaric,*
Tehran Suburb Education Organization, Chahardangeh Region, Tehran, Iran
b
c
a
Research on Pt complexes has been stimulated since the discovery of the anti-cancer drug cisplatin. However, cis-platin has two drawbacks; toxicity and the presence of resistance to the drugs.
Several PtIV complexes have been synthesized recently and shown high activity in vitro and in
clinical testing. [Pt(dpyam)Cl4].DMF (1) (dpyam is 2,2'-dipyridylamine) was prepared from the
reaction of H2PtCl6.6H2O with 2,2'-dipyridylamine in methanol. The same method was employed to
make [Pt(4,4'-dtbipy)Cl4] (2) (4,4'-dtbipy is 4,4'-di-tert-butyl-2,2'-bipyridine). These complexes
were characterized by elemental analysis; IR, UV-Vis, 1H NMR and 13C NMR spectroscopy and their
structures were studied by single-crystal X-ray diffraction method. Crystal data: for 1 at 100 K:
monoclinic, space group P21/c, a = 8.6834(5)Å, b = 11.1480(7)Å, c = 18.0959(11)Å, β =
100.5440(10)°, Z = 4, R1 = 0.0199 and for 2 at 293 K: monoclinic, space group P21/a, a =
20.9123(5)Å, b = 26.6946(6)Å, c = 25.6495(5)Å,
β =94.064(2)°, Z = 4, R1 = 0.0642. In
these complexes, PtIV ion is six-coordinated in a distorted octahedral environment. We report herein
introduced a new method for the synthesis of PtIV complexes starting with H2PtCl6.6H2O as a
starting material.
Keywords: PtIV; 2,2'-Dipyridylamine; 4,4'-Di-tert-butyl-2,2'-bipyridine; Crystal structure.
IICC12
61
P-57
Synthesis and characterization of Erbium oxide doped cadmium lead –borate glasses
A. Amini Ashan*, V.Golsanamlu
[email protected]
Department of Chemistry, University of Urmia, Urmia, Iran
Erbium doped cadmium lead borate glasses were prepared from melting in appropriate proportions
of a mixture of CdO, PbO2, H3BO3 and (1-2 mol %) Er2O3 in the temperature range of 800-850 °C.
The density of glass samples was measured using Archimedes Principle. The infrared spectra of the
glasses in the range of 400-4000 cm-1 showed their structure systematically. No boroxol ring
formation was observed in the structure of these glasses, but the conversion of 3-fold to 4-fold
coordination of boron atoms in the structure of glasses was observed. The glass transition studies
were done through differential scanning calorimetry. This glasses were prepared using annular
H3BO3, pbO2, CdO, and Er2O3 in the composition range XPbO2- (50-x-y) CdO-50H3BO3-y Er2O3
Where x = 30 and y = 0,1,2, respectively. The XRD patterns of this glasses do not show any sharp
peaks indicating the absence of crystalline nature. This confirms the amorphous nature of the
glasses. The optical absorption spectrum of 1 mol% this glass in the wavelength range 400-1000
nm is prepared. The following transitions are observed in the 400-1000 nm spectral region, from
the
ground state to the
,
,
+
,
,
+
,
+
+
excited states. The assignment of these transition has been made on the basis
and
of Carnall et al . This is due to the nephlauxetic effect which indicates the presence of Er-O
covalence in the glass system.
Keywords: Erbium; Cadmium; Lead borate glasses
P-58
Reaction of cyclometalated platinum(II) complexes with 1,1'bis(diphenylphosphino)ferrocene
Hashem amini*, S. Masoud Nabavizadeh, Mehdi Rashidi
Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, Iran
There have been great interests in synthesis and investigations of transition metal complexes
containing the biphosphine ligand 1,1'-bis(diphenylphosphino)ferrocene, dppf, as the complexes
have been involved in many catalysis, organic synthesis, electrochemical, materials science and
biological studies and applications. Reaction of each of the cyclometalated complexes [PtAr(CN)(SMe2)], 1,(Ar=ph, p-MeOC6H4, p-MeC6H4 and C-N=deprotonated 2-phenylpyridine or
benzo[h]quinoline) with 0.5 equiv of dppf yielded the binuclear Pt(II) complex [Pt2Ar2(C-N)2(µdppf)], 2, in a good yield. All the complexes were fully characterized using multinuclear (1H, 31P,
195
Pt) NMR spectroscopy. Complex [Pt2(p-MeOC6H4)2(bhq)2(µ-dppf)], 3, was further identified by
single crystal X-ray structure determination, the first report for a Pt dimer complex bearing a dppf
as spacer ligand. The course of reaction involving the complex [Pt(p-MeC6H4)(ppy)(SMe2)], 1b, as
followed by low temperature 31P NMR spectroscopy to characterize intermediates and the
mechanism of this reaction. When the starting complex [Pt(p-MeC6H4)(ppy)(SMe2)], 1b, was reacted
with 1 equiv of dppf, the course of the reaction was different and a mixture containing complexes
2b,free dppf, and a new species C was formed. Complex C is suggested to obtain by the reaction of
complex A with complex B on the basis of 31P NMR spectroscopy.
Keywords:
temperature
31
Cyclometalated
P NMR.
Complex,
1,1'-bis(diphenylphosphino)ferrocene
(dppf)
,
low
62
IICC12
P-59
Oxidation of alkanes with hydrogen peroxide catalyzed by novel complex of oxoperoxo
Molybdenum(VI)
a
M. Aminia, M. Bagherzadeha*
Complexes of various transition metals and particularly organometallic derivatives are well-known
catalysts for oxidations of hydrocarbons with peroxides, predominantly hydrogen peroxide.
Oxoperoxo complexes have been intensively investigated as oxidation catalysts, particularly for
epoxidation of alcohols and olefins. A new mononuclear oxo-peroxo complex of Molybdenum(VI) of
the formula [MoO(O2)(ox)2] (where ox = 2-(2'-hydroxyphenyl)oxazoline) have been synthesized and
characterized by X-ray structure analysis, elemental analysis, infrared, UV–visible and 1H, 13C NMR
spectroscopy. Here, we have explored the possibility of complex [MoO(O2)(ox)2] to catalyze
oxidation of alkanes with hydrogen peroxide. The results show complex [MoO(O2)(ox)2] is very
efficient catalyst for the oxidation of a variety of alkanes to the corresponding alcohols and ketones
with maximum selectivity.
Keywords: Alkanes, Oxidation, Molebdenum(VI), Oxo-peroxo
P-60
Synthesis, X-ray structure, characterization and catalytic activity of a new polymeric
manganese(II) complex with iminodiacetate
M. Aminia, M. Bagherzadeh, D. M. Boghaeia, M. M. Najafpourb
b
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan, Iran
a
Sulfoxides and aldehydes are useful reagents in organic synthesis and they are also valuable
synthetic intermediates in the preparation of chemically and biologically active compounds. A new
polymeric manganese (II) complex with the general formula {Mn(O2CCH2NH2CH2CO2)2(H2O)2}n of
reaction of the iminodiacetatic acid and manganese(II) perchlorate under nitrogen in water, has
been synthesized and characterized. The structure of the newly synthesized complex was
determined using single-crystal X-ray diffraction, elemental analysis, IR and UV-Vis spectra. This
complex exhibited excellent catalytic activity and selectivity for oxidation of various alcohols and
sulfides to the corresponding aldehydes/ketone and sulfoxides using oxone (2KHSO5·KHSO4·K2SO4)
and H2O2 respectively as an oxidant under air at room temperature. Easy preparation, mild reaction
condition, high yields of the products, short reaction time, no over-oxidation products, high
selectivity and inexpensive system make this catalytic system a useful method for oxidizing of
various alcohols and sulfides.
Keywords: Manganese(II); Crystal structure; Iminodiacetate; Alcohol; Sulfide; Oxidation
IICC12
63
P-61
Synthesis and catalytic properties of benzimidazole and benzoxazoline
dioxomolybdenum(VI) complexes in olefins epoxidation and sulfides oxidation
a
M. Aminia, R. Salamia, M. Bagherzadeha*
The fact that molybdenum is essential metallic element and exhibit significant enzymatic role in
biochemical reactions especially in the oxidation of aldehydes, purines and sulfides has created
enormous interest to use the molybdenum complexes as biomimetic catalysts in the oxygenation of
organic compounds. In this study, two new complexes of cis-dioxomolybdenum (VI)-banzimidazole
and cis-dioxomolybdenum (VI)-banzoxazolin were synthesized and these characterized with NMR,
IR, UV-Vis spectroscopies and CHN analysis. The catalytic reactivity of synthesized complexes was
investigated for epoxidation of olefins and oxidation of sulfides. The effect of the reaction conditions
on the oxidation was studied by varying the amount of the catalyst, reaction temperature, reaction
time and the amount of oxidant. These complexes exhibited high activity and selectivity for
epoxidation of olefins at temperature 70 oC and reaction time 60 min and a good yield were
obtained for oxidation of sulfide at room temperature and reaction time 15 min.
Keywords: Molybdenum(VI), Banzimidazole, Banzoxazolin, Oxidation, TBHP, UHP.
P-62
Production of Samarium Metalo-Organic Radiopharmaceuticals for Targeted Therapy
Applications in Nuclear Medicine
Z. Naseri a , A. Nemati Kharat a,*, A. R. Jalilianb
School of Chemistry, University College of Science, University of Tehran, Iran
Nuclear Science and Technology Research Institute, P.O.Box: 11365-8486, Tehran, Iran
a*
b
Schiff bases are ligands which play an important role in the coordination chemistry of many
transition metals due to the ease of their formation and versatility. Metal complexes of Schiff bases
found use in bioinorganic chemistry as models for metal containing sites in metalloproteins, as
catalysts for some organic reactions, or in magneto chemistry. The condensation of o(diphenylphosphino) benzaldehyde and various chiral diamines gives a series of diimino-diphosphine
tetradentate ligands, which are reduced with excess NaBH4 in refluxing ethanol to afford the
corresponding diamino-diphosphine ligands in good yield that were characterized by IR and NMR
spectroscopic methods. A series of these ligands was labeled with 153Sm that formation of these
complexes was validated with RTLC. Optimazation of factors affecting labeling (pH, Metal to Ligand
ratio, etc.) leads to a labeling yield higher than 90%. In this study, stability of radionuclide was
measured in human serum and for investigation of biodistribution in different tissues and comparing
with normal tissue, SmCl3 and labeled compounds were injected to the tail vein of a normal and
tumor tissue of rat then absorption dose determined at rat tissue. These compounds are suitable in
order to overcome the metastatic bone pains.
Keywords: Samarium, Schiff base, Radiopharmaceutical, Therapy.
64
IICC12
P-63
Synthesis and Characterization of HMX Polymorphs
a, b
S. Amiry a,* ,M. Lashanizadegan b, Y. Bayat c
Department of Chemistry, Alzahra University, Tehran, Iran.
c
Malek Ashtar University of Technology, Tehran, Iran.
1,3,5,7- tetranitro-1,3,5,7- tetracyclo octane (HMX) is one of the most powerful chemical explosives
that manufactured. Because of its thermal stability and high detonation velocity relative to other
explosives, used in the warhead, bursting charges, fuses, mines, production of oil well detonation
(Well perforation) and etc. HMX appears in four modification α, β, γ, δ that produced in special
temperature and solvents. These conformers have different structures, unit cells and space group,
so their properties are different. Todays raw HMX prepared in Iran, it is thus very important to
understand what kind of conformers has obtained. There are not information about production of
pure conformers and the role of solvent on the nature of the polymorphs. In the present study we
have prepared the various polymorphs and obtained the best method. Also we study about lattice
constants and record SEM, Raman, IR, XRD, DSC spectra of polymorphs then compared data with
each others and confine their difference.
Key words: HMX, Polymorph, α -HMX, β- HMX, γ-HMX, δ-HMX
P-64
Synthesis, Stereochemistry and Solution Dynamics of Allyl-Palladium Homobimetallic
Complexes Containing Secondary Dithiooxamides as Binucleating Ligands
H. Amiri Rudbari, G. Bruno, F. Nicolò and S. Lanza*
Dipartimento di Chimica Inorganica, Chimica Fisica e Chimica Analitica, Unversità di Messina, Salita
Sperone 31 Contrada Papardo, 98166 Messina, Italy
Depending on the experimental conditions, the reaction between [(η3-allyl)PdCl)2 and secondary
dithiooxamides H2R2C2N2S2 gives rise to binuclear complexes having topologies I and II. The
stereochemistry of type I and II compounds has been determined both in the solid state (RX) and
in solution (stereochemical analysis by means of chiral auxiliaries). Temperature produces rapid allyl
isomerization. This allyl movement requires [1, 2]: a) dissociation of one Pd-N bond, b) rotation
around the remaining Pd-N bond, c) isomerization of T-shaped intermediate and d) remaking of the
Pd-N bond. It has been shown that type I and II compounds exist in solution as an equimolar
mixture of endo and eso isomers (ally cuspids directed toward the same side or toward opposite
sides of molecular plane respectively), while in the solid state the eso isomer is slightly prevalent.
Keywords: Homobimetallic
pseudorotation, X-ray
complexes,
secondary
dithiooxamides,
Allyl-palladium,
Alllyl
IICC12
65
P-65
Coordinating Properties of Schiff Base Polytopic Ligands Prepared from Chiral
Precursors
(E-mail): [email protected]
1,2-bis(2'-nitrophenoxy)-4- methylbenzene is a chiral molecule due to the high barrier to the
rotation of nitrobenzene groups. This compound is easily transformed into a diamine, which reacts
with 2-pyridinecarboxaldehyde and gives rise to a bichelating Schiff-base ligand. This latter, on
reaction with zinc (II), provides the following complex. In the complex, the basic structure of the
precursor dinitro compound has not changed. This means that the free Schiff-base ligand is formed
with the same configuration of its dinitro precursor. As a consequence, a given metal ion can be
coordinated by the said ligand only according to the ligand configuration. Schiff base ligands
prepared from structurally rigid chiral diamines could give rise to octahedral complexes of
predetermined configuration.
Keywords: Rigid chiral diamines, Schiff-base ligand, Octahedral complexes, X-ray
P-66
Pseudochiral-at-Metal Organopalladium Complexes
The
meso-dithioxamide
H-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl)-H
(H2mesoDTO) bonds [(η3-allyl)-palladium(II)]+ fragment and provides the Cs symmetrical complex [(η3allyl)palladium(H-mesoDTO -S,S-Pd)], which is pseudochiral at metal and exists as a mixture of
two symmetrical mesoforms. When the metal fragment bonded by the said meso-dithiooxamide is
[(η3-crotyl)-palladium(II)]+, the resulting complex [(η3-crotyl)palladium(H-mesoDTO
 -S,S Pd]
possesses a chiral plane and a pseudochiral center, and therefore the complex is a mixture of two
enantiomeric pairs. Also, H2-mesoDTO bonds through sulphur chelating system a [(tri-npropylphosphine)chlorido-palladium(II)]+ moiety, and gives rise to [(tri-npropyl-posphine)ClPd(HmesoDTO -S,S Pd)] as a racemate. The above racemate acts as a metallo-ligand and bonds a
[(η3-allyl)-palladium(II)]+ fragment through its nitrogen chelating system and provides the complex
-S,S Pd(chlorido-phosphine)
-N,N Pd-allyl)Pd(η3[(tri-npropyl-phosphine)ClPd(µ-mesoDTO
allyl)]. This bimetallic complex possesses a chiral plane and a pseudoasymmetric metal center and
therefore it is mixture of two enantiomeric pairs. The absolute configuration of the pseudochiral
palladium center in such a complex has been determined. Finally we tried to join a [(η3-crotyl)palladium(II)]+ fragment to the [(tri-npropyl-posphine)ClPd( -mesoDTO -S,S Pd)] racemate, in
an attempt to obtain a bimetallic complex with three stereogenic elements, but the only compound
which we are able to identify was the homobimetallic complex [(tri-npropyl-posphine)ClPd-(HmesoDTO
-N,S Pd)PdCl(tri-npropyl-phosphine]. This work gets insight into stereochemistry of
coordination compounds, in that pseudochirality is an argument quite neglected in inorganic
chemistry. Furthermore, [(tri-npropyl-phosphine)ClPd(µ-mesoDTO -S,S Pd(chlorido-phosphine) N,N Pd-allyl)Pd(η3-allyl)] is the first compound in which the absolute configuration of a pseudochiral
metal center has been determined.
Keywords: Meso-dithioxamide, Palladium complexes, Pseudochirality, X-ray
66
IICC12
P-67
Adsorption of Cerium ion from aqueous solutions using chemically modified sawdust by
nano layer of conducting polymers
R. Ansari*, A. Mohammad-khah, A. Pornahad
In this investigation, adsorption of Ce (IV) ions, a superheavy rare earth element by the selected
adsorbents: chemically modified sawdust by coating of polypyrrole, polyaniline and polythiophene
conducting electroactive polymers (termed as, PPy/SD, PAni/SD and PTh/SD) was studied. In order
to have a good comparison, uncoated sawdust and two commercial grades of activated carbon
(both powdered and granulated forms) were also used for testing at the same time. In order to find
out the optimized adsorption conditions, the effect of some important parameters affecting the
sorption efficiency of the selected adsorbents such as sorbent dosage, initial concentration, and
contact time for uptake of Ce (IV) ions was studied. The sorption experiments were carried out in
both batch and column systems. Adsorption isotherms were discussed using Freundlich and
Langmuir equations. Among the selected adsorbent used for uptake of Ce (IV), PPy coated onto
sawdust showed excellent sorption capacity.
Keywords: Adsorption, Ce (IV), sawdust, activated carbon, conducting polymers, nanocoating
P-68
Anticooperativity in Dihydrogen Bonded Clusters of Ammonia and BH4-1
MASUME ARABPOUR,ABEDIEN ZABARDASTI*and NAHID ZARE
Dihydrogen bonds (DHBs) have been investigated extensively by experimental as well as the
theoretical methods Typically, the DHB occurs between positively and negatively charged hydrogens
and designated as X-H +… -H-Y system, where X-H is the typical proton donating bond and the
second negatively charged hydrogen atom is the proton acceptor. One of the important aspects of
the DHBs as driving forces in molecular associations is their cooperativity or anticooperativity when
increasing the number of H…H contacts in the self-association of molecular systems leads to
additional energy, calculated on the basis of one dihydrogen bond.(1)In this research ab initio
calculations were used to analyze the DHB interactions of BH4-1 as hydrogen bond acceptor with
NH3 and H2O as hydrogen bond donor.(2) Calculations were carried out at the MP2/6-311++G(d,p)
and B3LYP/6-311++G(d,p) computational levels. (3)The stabilization energy and cooperativity
energies of dihydrogen bonded clusters of the type BH4(NH3)n-1 and BH4(H2O)n-1 where n=1- 4 have
been calculated. Stability of clusters enhanced with the cluster growing in contrast the cooperativity
decreased with increasing the size of clusters. Blue Shift of the B-H stretching frequency in the DHB
complexes has been predicted. From comparisorm of B(NH3)n-1 clusters with B(H2O)n-1 clusters it
can be concluded that B(H2O)n-1 are were stable than B(NH3)n-1.The topological analysis of the
electron density of optimized structures was done using the Atoms in Molecules (AIM) methodology.
Keywords: Dihydrogen bonded clusters, Anticooperativity, Blue shift dihydrogen bonding, BH41-
IICC12
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P-69
Acidity of HCNO, HNCO, HONC, HOCN: a treatment from the viewpoint of ab initio
approach
MASUME ARABPOUR,ABEDIEN ZABARDASTI* and NAHID ZARE
The pKa (_lgKa) values have been calculated using density functional theory (DFT). The polarized
continuum model (PCM) is used to describe the solvent(1). Using these methods, we successfully
predicted the pKa of The fulminic acid (HCNO)1 and its isomers isofulminic acid (HONC), cyanic acid
(HOCN) and isocyanic acid (HNCO)(2),in aqueous with the average error of 0.5 in pKa units. Two
different thermodynamic cycles have been studied. The theoretical valuesThe model furnishes pKa
values in relatively good agreement with experimental data. The electronic structures of the
molecules HCNO, HNCO, HONCO, HOCN and their anions -OCN, CNO- have been investigated at
the gas phase as well as in the aqueous solution by density functional theory method at B3LYP/6311++G(d,p) level(3). The thermodynamic stability of the HNCO and HCNO molecules was shown
to be higher than that of the HOCN and HONC molecules, respectively. The following series of the
alteration of the protolytes strength HONC > HOCN > HNCO> HCNO was predicted. The
computations reflect the general sequence of change in the proton-donor propertiesHONC > HOCN
> HNCO > HCNO, coinciding with the order of descending hydrophobicity of the compounds. The
comparative proton-donor ability of the above acids in aqueous solutions is determined basically
from the electronic structure and atomic arrangements in the corresponding molecules and anions
that affected their atom group electronegativities.
Keywords: Density functional theory; PCM, pKa, Fulminic acid, Isocyanic acid
P-70
Synthesis and Characterization of Zn(II) and cd(II )Transition Metal Complexes with5(2-phenyl-1-diazenyl)-2-{[(2-sulfanylphenyl)imino] methyl}-1-benzenol
MASUME ARABPOUR,ABEDIEN ZABARDASTI*,ALI KAKANEJADIFARD and NAHID ZARE
Schiff bases and their transition metal complexes because of their catalytic, antifungal and
antibacterial activities as well as other applications in chemistry have been subject of a lot of
studies. In this work we present the preparation of a shiff base and its complexes with some
transition metal ions.[1] The Schiff base ligand
5-(2-phenyl-1-diazenyl)-2-{[(2sulfanylphenyl)imino]methyl}-1-benzenol (H2L) was synthesized from reaction of2-aminothiophenol
and 1_(3_formyl _4_hydroxy phenyl azo) banzen in the ethanol as a solvent. H2L was characterized
by means of FT-IR, UV-Vis, 1H NMR, and 13C NMR methodst.[2]From reaction of H2L with Zn(II),
cd(II) related transition metal complexes were prepared. Complexes have been characterized by IR,
UV-Vis, 1H NMR, and 13C NMR techniques.
Keywords: Mononuclear Zn (II) and cd(II) complexes, Schiff base
68
IICC12
P-71
Synthesis and Characterization of Zn(II) and Hg(II )Transition Metal Complexes with 5(2-(4-methyl phenyl)-1-diazenyl)-2-{[(2- sulfanylphenyl)imino] methyl}-1-benzenol
MASUME ARABPOUR,ABEDIEN ZABARDASTI*,ALI KAKANEJADIFARD and NAHID ZARE
Schiff bases and their transition metal complexes because of their catalytic, antifungal and
antibacterial activities and other applications in chemistry have been subject of a lot of studies. In
this work we present the preparation of a shiff base and its complexes with some transition metal
ions Schiff base ligand 5-(2-(4-methylphenyl)-1-diazenyl)-2-{[(2-sulfanylphenyl)imino] methyl}-1benzenol (H2L) was synthesized from reaction of 2-aminothiophenol and 1_(3_formyl _4_hydroxy
phenyl azo)_4methyl banzen in the ethanol as a solvent. H2L was characterized by means of Ft-IR,
UV-Vis, 1H NMR, and 13C NMR methodst From reaction of H2L with Zn (II), Hg(II) related transition
metal complexes were prepared. Complexes were characterized by IR, UV-Vis, 1H NMR, and 13C
NMR techniques.
Keywords: Mononuclear Zn(II) and Hg(II) complexes, Schiff base
P-72
Efficient ring opening of epoxides with amines catalyzed by Fe-substituted WellsDawson type polyoxometalate
a
N. Aramesha, B. Yadollahia,*, v. Mirkhania
*E-mail address: yadollahi@chem,ui.ac.ir
Polyoxometalates (POMs), as metal–oxygen cluster species, have obtained extensive attention due to
not only the structural diversity but also their attractive properties, such as catalytic activity
magnetism, photochemical activity and electrical chemistry. The catalytic function of heteropoly
compounds has been attracted much attention and both homogeneous and heterogeneous catalysi
are possible. Because of the large size and the high charge, the Wells-Dawson type polyoxometalate
are used as catalysts. Epoxides are important intermediates in organic synthesis and there are well
known carbon electrophiles capable of reacting with various nucleophiles. The aminolysis of epoxide
gave aminoalcohols that are an important class of organic compounds. They are used as building
blocks for the synthesis of pharmaceuticals, insecticidal agents and chiral ligands for asymmetri
catalysis. In this work, Fe-substituted Wells-Dawson type polyoxometalate was synthesized and used
for efficient ring opening of epoxides to the corresponding aminoalcohols. Various epoxides were
converted into the corresponding aminoalcohols with different aromatic amines. The reactions were
carried out at room temperature and high to excellent yields were obtained.
Keywords: Wells-Dawson polyoxometalate; ring opening; epoxide; amines
IICC12
69
P-73
Catalytic oxidation of sulfides by hydrogen peroxide in the presence of transition metal
substituted Keggin type polyoxometalate supported on Dowex
Z. Aramesh, B. Yadollahi* and Sh. Tangestaninejad
Department of chemistry, University of Isfahan, Isfahan 81746-73441, Iran
(e-mail: yadollahi@chem,ui.a.ir)
Among a wide variety of heteropoly compounds, the Keggins are the most stable and more easily
available. The Keggins heteropoly anions are typically represented by the formula [XM12O40]x-8,
where X is the heteroatom, x is its oxidation state, and M is the addenda atoms (usually Mo6+ or
W6+). Supporting the heteropolyacids on solids with high surface area, improved their catalytic
performance in various liquid-solid heterogenous reactions. The supports usually used in catalysis
are metal oxides, activated carbon, polymers, silica or zeolites. Important features of polymers are
good mechanical properties, good thermal stability and low solubility in the environment reaction.
Sulfur compounds in fuels have been a major source of air pollution. On the other hand, sulfoxides
and sulfones are important intermediate in the synthesis of chemical and biological molecules. The
most common strategy for preparation of these compounds is sulfides oxidation. In this work, we
want to report oxidation of sulfides with H2O2 by Keggin type polyoxometalate supported on
polymer Dowex. Optimization of the reaction conditions such as type of solvent, amount of catalyst
and amount of oxidant can be provided suitable conditions for oxidation of sulfides. Oxidation of
various sulfides investigated and high to excellent yields was obtained.
Keywords: Keggine Polyoxometalate, Oxidation, Hydrogenperoxide, Sulfide, sulfoxide, sulfone.
P-74
Kinetic Studies of the Interaction Between Organotin(IV)chlorides and Tetraaza Schiff
Bases
Zahra Aasdi*
Chemistry Department, College of Sciences, Shiraz University, Shiraz, I.R. Iran
E-mail address: [email protected], [email protected]
Organotin(IV) complexes have been the subject of interest because of their biological and
commercial application. In recent years, there have been more and more reports on the synthesis,
anti-tumor activities and structural elucidations of various diorganotin Schiff bases. Increasing
attention has also been devoted to the organotin(IV) complexes with Schiff base ligand in view of
their special anti-tumor activities. The observation that transition metal Schiff base complexes can
function as neutral donor ligand, has led to several investigations of their reactions with tin Lewis
acids and to the isolation of the adducts. The kinetics of the interaction between the teteraaza
Schiff bases: (Me4-Bzo2[14]tetraeneN4) (tmtaa), (Me4-4-CH3Bzo2[14]tetraeneN4) (Metmtaa), (Me4-4ClBzo2[14]tetraeneN4)
(Cltmtaa)
that
[(Me4-Bzo2[14]tetraeneN4)]
is
(
5,7,12,14tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)
(tmtaa)
as
donor
with
organotin(IV)chlorides: methyltin(IV)trichloride, phenyltin(IV)trichloride, dimethyltin(IV)dichloride,
diphenyltin(IV)dichloride and dibutyltin(IV)dichloride as acceptor were studied in acetonitrile. The
kinetic parameters and the second order k2 rate constants show the donor properties of tetraaza
Schiffbases
as:
Me4-4-CH3Bzo2[14]tetraeneN4
>
Me4-Bzo2[14]tetraeneN4
>
Me4-4ClBzo2[14]tetraeneN4 and also the acceptor properties of organotin(IV)chlorides as: PhSnCl3 >
MeSnCl3 > Ph2SnCl2 > Me2SnCl2 > Bu2SnCl2. An excellent linearity of kobs vs. the molar
concentration of the acceptor, the high span of k2 values ,the large negative values of ∆S≠ and low
∆H≠ values suggest an associative (A) mechanism for the acceptor-donor interaction.
Keywords: Kinetic, Mechanism, Organotin(IV)chlorides, Tetraaza Schiff base.
70
IICC12
P-75
Synthesis and Characterization of new Hydrazone Schiff base Ligand from
Phenanthroline
Nasim Asghari Lalami and Hassan Hosseini Monfared *
Department of chemistry, Zanjan university 45195-313, zanjan, Islamic Republic of Iran
The synthesis and structural investigation of new ligands and their metal complexes have received a
renewed attention in recent years. Hydrazone ligands have interesting ligation properties because
of the presence of several coordination sites. Moreover, they form a class of compounds with a
wide range of biological activity as remarkable anticancer, amoebicidal, antibacterial, antimicrobial,
antineoplastic, antiviral, anti-inflammatory, antitumor, antileukemic, and enzymatic reaction
inhibitors. Metal complexes with Schiff base ligand have played an important role science the early
days of coordination chemistry. Hydrazone Schiff base has long been paid considerable attention for
its fascinating chemical behavior and biological essentiality. Of interest to structural chemist is the
coordination ability of hydrazone ligand through the nitrogen or oxygen electron-donating atoms
that allows it serve as either multidentate or bridging building block in structural assemblies. In this
study we have synthesized 1,10-phenanthroline-5,6-dione from 1,10-phenanthroline in the presence
of H2SO4, HNO3 and KBr, followed by extraction with chloroform. Then, from the reaction of molar
ratio of methanolic solution of dione with methanolic solution of benzhydrazide the related Schiff
base (scheme1) with good yield was synthesized. This ligand which was characterized with FT-IR,
1
H NMR and 13C NMR spectroscopy. can be used in formation of many metal complexes.
Keywords: 1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, Hydrazone, Schiff base.
P-76
Synthesis and characterization of a new Pb(II) coordination polymer based on the
Polypyridy ligand 4'-(4-pyridyl)-2,2':6',2"-terpyridine
a
Tahereh Asgharia, Akbar Ghaemia,*
Department of Chemistry, Islamic Azad University, Saveh Branch, P.O. Box 39187-366, Saveh, Iran
Crystal engineering of coordination polymers with fascinating structures has attracted a great deal
of attention in the recent years because of their potential as functional materials. Self-assembly of
organic ligands and inorganic metal ions is one of the most efficient and widely utilized approaches
for the construction of such polymers. However, a major challenge in this approach is the
predictability of the polymeric structures since many factors such as coordination geometry of the
metal, nature of the ligands, metal-to-ligand ratio, solvent system, template, pH value of solution,
and counter-ions will influence the framework formation. Thus, systematic researches are required
for understanding the roles of the factors in the formation of frameworks. 4'-(4-pyridyl)-2,2':6',2"terpyridine (n-pytpy) (n = 2, 3, 4) ligands have been of our research interest for their particular
characteristics described as following. (a) These ligands contain two distinct coordination domains
that can be used as either tridentate chelating ligand or mono-tridentate bridging ligand. (b)
pyterpy can acts as both hydrogen-bond acceptors and donors due to the presence of pendent
pyridyl nitrogen and hydrogen atoms construct supramolecular framworks. (c) The aromatic rings
usually show a tendency to participate in intermolecular π…π interactions which many significantly
effect the packing arrangement of the structure. In this work [Pb(4-pytpy)(SCN)2]n compound has
been synthesized from the reaction between 4'-(4-pyridyl)-2,2':6',2"-terpyridine (pyterpy) ligand
and KSCN as counter-ions with Lead(ll) acetate in methanol solvent. This new Lead(ll) coordination
polymer has been characterized by elemental analysis, IR spectroscopy.
Keywords: Coordination polymers, 4'-(4-pyridyl)-2,2':6',2"-terpyridine, Lead(ll), Polypyridy ligand.
IICC12
71
P-77
Synthesis and characterization of a new Hg(II) coordination polymer based on the
Polypyridy ligand 4'-(4-pyridyl)-2,2':6',2"-terpyridine
a
Tahereh Asgharia, Akbar Ghaemia,*
Department of Chemistry, Islamic Azad University, Saveh Branch, P.O. Box 39187-366, Saveh, Iran
Coordination chemistry of the multitopic ligand of 4'-(4-pyridyl)-2,2':6',2"-terpyridine (pyterpy) has
been recently attracting growing attention in the design of the supramolecular building blocks based
on the metaldirected self-assembly. This ligand contains one widely used 2,2':6',2"-terpyridine
(terpy) coordinative site and another pyridyl site at the 4'-position, these two sites are able to bind
with different metal ions, thus leading to the coordination polymers with various frameworks. The
design and synthesis of metal-organic frameworks (MOFs) have attracted intense interest from the
viewpoints of the development of new functional materials with unique properties for potential
applications in a wide variety of fields, such as catalysis, molecular recognition, separation and
nonlinear optics. Many of one -, two-, and three-dimensional coordination polymers have been
generated from transition metal templates with rigid and flexible pyridyl containing bidentate or
multidentate organic spacers. In this process many factors may affect the formation and crystal
growth of products such as the inorganic counter–ions and the metal to ligand ratio, solvent and
temperature. In this work [Hg(4-pyterpy)Cl2]n compound has been synthesized from the reaction
between 4'-(4-pyridyl)-2,2':6',2"-terpyridine (pyterpy) ligand and NH4OAc as counter-ions with
mercury(ll) chloride in methanol solvent (the branched tube method). This new mercury(ll)
coordination polymer has been characterized by elemental analysis, IR spectroscopy.
Keywords: Coordination polymers, 4'-(4-pyridyl)-2,2':6',2"-terpyridine, Mercury(ll), Polypyridy
ligand.
P-78
Efficient biomimetic oxidation of alcohols with (Diacetoxyiodo)benzene catalyzed by
metalloporphyrins: Effect of metals, meso-Substituents, and anionic axial ligands
Gholam Reza Karimipourb, Leila Ashnaa,*, and Mohamad Hadiana
Department of Chemistry, Islamic Azad University, Gachsaran Branch, E-mail:
[email protected]
& [email protected]
b
Department of Chemistry, Yasouj University, Yasouj, E-mail: [email protected]
a
In this work, we first investigated the ability of metalloporphyrins with different metal centers,
counter ions, and meso-aryl substituents as catalysts in the oxidation of benzyl alcohol in the
presence of (diacetoxyiodo)benzene (PhI(OAc)2). Manganese porphyrin/(PhI(OAc)2 is an efficient
biomimetic system for catalytic oxidation of benzyl alcohol in the presence of imidazole. While the
steric properties of porphyrin complexes and axial nitrogenous bases used in this study are of
paramount importance in determining the overall catalytic reaction time and oxidation yield, clear
evidence is provided that only the manganese porphyrins are able to catalyze oxidation of benzyl
alcohol, whereas the Fe, Ni and Co complexes have no acceptable catalytic activities. Manganese
porphyrins with electronwithdrawing substituents on their phenyl groups are much less effective
catalysts than those with electron donating substituents, so that the most efficient system that has
been selected involves Mn(T(4-CH(CH3)2P)P)OAc, which was then used for oxidation of other
alcohols. This method provides a cost-effective and environmentally friendly oxidation procedure
due to the utilisation of less toxic PhI(OAc)2. The amounts of the products (%) and the selectivities
are very dependent electronic and steric properties of the starting alcohols. The reaction times were
5-15 minutes with yields of 85-95%.
Keywords: Alcohols; Catalytic oxidation; Manganese porphyrin; (Diacetoxyiodo)benzene.
72
IICC12
P-79
Simple Method for Manufacturing High Purity Micro and Nano Calcium Carbonate
Particles
F. Ashouria*, M. Kambaranib, , A. Rinehb
Department of Chemistry, Sharif university of technology, Tehran, Iran
b
Farayand Chemical Research Group, ACECR Tehran branch, College of Engineering, Tehran
university, Tehran, Iran
a
Various nanoparticles have such important roles, as being functional inorganic fillers that are widely
used in plastics, rubber, magnetic, paint and paper industries, etc [1]. The size of ultrafine CaCO3,
which belongs to nanoparticles is usually from 0.02 to 0.1 µm, [2] .This study focuses on the
preparation of high purity micro and nano-sized precipitated calcium carbonate (PCC). Nano-Pcc
was prepared by using mineral carbonate calcium (lime stone), Nitric acid, Carbon dioxide and
Monoethanolamine as a dispersing agent. The size and shape of particles were measured by means
of scanning electron microscopy (SEM). The result shows that temperature, pressure of gas and
monoethanolamine concentration have strong effect on particles size and yield of product so these
parameters were optimized in this work. The use of low-cost raw industrial materials and
manufacture of high purity product are the advantages of this study.
Keywords: Nano particles, Calcium carbonate, Monoethanolamine, SEM.
P-80
Synthesis and characterization of new Schiff base calixarene and its complexes with
Cu(II),Ni(II)
A. Masoud Asl, B. Shaabani*
Faculty of Chemistry, Tabriz University, Tabriz, Iran
e-mail: [email protected]
Calixarenes, a well-known family of macrocyclic phenol-formaldehyde oligomers, have been
attracting the interest of chemists for more than three decades. As these compounds represent
readily available and precisely defined three-dimensional structures, they found numerous
applications in supramolecular chemistry. The unproblematic derivatization of the calix[4]arene
skeleton together with the controllable shape of the cavity makes this molecule an ideal molecular
scaffold for the construction of various receptors. Due to their excellent complexation abilities,
calix[4]arenes are frequently used for the design of novel selective complexation agents. Depending
on the substitution pattern and the conformation, calix[4]arenes bind cations, anions and neutral
compounds. Here we report synthesis of new Schiff base calix[4]arene bearing two imine pendants
at lower rim and its complexes with Cu(II) and Ni(II). Schiff base ligand has been prepared via
condensation reaction between 1,3-diaminocalix[4]arene and 5-Brom-2-hydroxybenzaldehyde by
refluxing in ethanol. Complexes were synthesized by treating an ethanolic solution of ligand with
equimolar amount of transition metal salts. These compounds have been characterized by IR,
HNMR, UV-VIS, elemental analysis and conductometry. Comparison of spectroscopic results for the
ligand and complexes also conductometric data and Vis absorption spectra for complexes
suggest that ligand act as a tetra dentate and coordinate via two imine nitrogen and two ether
oxygen of aldehyde.
Keywords: Calix[4]arene, Complex, Ligand, Schiff base.
IICC12
73
P-81
Synthesis and characterization of nanocrystalline tin oxide by hydrothermal method
M.Asl, B.Shabani*
Department of Chemistry, University of Tabriz,Tabriz , Iran
Nanocrystalline materials with average graine size of less than 50 nm have attrached considerable
scientific interest because of their peculiar structures and unusual physical and chemical
properties.The microstructure of nanocrystalline materials depends upon the method of preparation
. Tin oxide ,a stable and large band-gap semiconductor , has excellent photo-electronic properties
and good sensitivity to gases. It is well known for its application in gas sensors and dye-based solar
cells . A simple gel to crystal conversion route has been followed for the preparation of ultrafine
SnO2 particles at 80-100◦C under refluxing conditions freshly prepared Tin hydroxide gel is allowed
to crystallize under refluxing and stiring conditions for 4-5h. Formation of nanocrystallites of SnO2 is
confirmed by x-rey diffraction (XRD) study . The thermal decomposition of Tin hydroxide yields
SnO2 only at 600 ◦C. This shows the advantage of the present method accordins to SEM and XRD
studies the average size of these particles is found to be ~20-25 nm
Keywords:Tin oxide ; Nanocrystallite;Gas sensors ; X-rey diffraction
P-82
Synthesis, spectral characterization, properties and structural analysis of Platinum(II)
complexes
Nafiseh Attari a,*, Saeed Dehghanpour b , Ali Mahmoudi a
Department of Chemistry, Islamic Azad University, karaj, karaj Branch, Iran
a
b
Four platinum(II) complexes, [PtCl2L] (L = (4-fluorophenyl)pyridin-2-ylmethylene-amine, 1; (4chlorophenyl)pyridin-2-ylmethyleneamine, 2; (4-bromophenyl)pyridin-2-ylmethyleneamine, 3 and
(4-iodophenyl)pyridin-2-ylmethyleneamine, 4) have been synthesized and characterized by CHN
analysis, IR and UV–Vis spectroscopy. The interesting photochemical and photophysical properties
of platinum(II) complexes have been thoroughly investigated . The reaction of the ligands with
[PtCl2(CH3CN)2] yields complexes [PtCl2(L)2]. Elemental analysis confirms the named stoichiometries
of all complexes. The IR spectra in the 4000–400 cm-1 range show that the ligand is coordinated to
the Pt(II) ions. The most striking bands of diimine ligands (ν(C=N)) decrease in frequency when
they are part of the complexes . The 1H resonances of the coordinated ligands are commonly
observed in complexes 1–4. Aside from the aromatic H-atoms, which appear at 7.27–7.87 ppm, the
imine protons appear as a singlet at 9.32– 9.34 ppm. The downfield shift of the imine protons
relative to the free ligands can be attributed to the deshielding effect resulting from the
coordination of the metal by the ligands . The 195Pt NMR spectra of the platinum Schiff base
complexes show signals at -2212 ppm for 1, -2211 ppm for 2, -2209 ppm for 3 and -2206 ppm for
4. The electronic spectra of the complexes were recorded in the 700–200 nm range. The spectral
data is presented in Table 1. The absorption spectra of all complexes exhibit a broad band close to
425 nm. This lowest energy feature in each case is the metal-to-ligand (PtII imine π*) charge
transfer (MLCT) transition. The redox behavior of the complexes in CH3CN solution was examined
by cyclic voltammetry. In general, these complexes show two reduction waves at potentials ranging
from -1.75 to -1.12 V).
Keywords: Diimine, electronic spectra ,NMR, UV–Vis
74
IICC12
P-83
Synthesis and characterization of three new Bis-quinazolines complexes derived from
2-((4-(2-aminobenzylamino)butylamino)methyl)benzenamine and 2hydroxybenzaldehyde
a
c
R. Azadbakhta,*, S. Menatib , R. Golbodaghic and M. Khdabandeha
Department of Chemistry, Payame Noor University, Hamedan, Iran
b
Department of Chemistry, Azad university, Khorramabad, Iran
Department of Chemistry, Payame Noor University, Toyserkan, Iran
Quinazolines are a class of fused heterocycles that contain the pyrimidine nucleus in their structure.
The presence of pyrimidine nucleus in these compounds often leads to very interesting biological
and
pharmaceutical
activities
especially
anti-inflammatory,
anticonvulsant,
diuretic,
antihypertensive, hypnotic, antimalarial, etc. Recently the quinazolines have been found to possess
potent phosphodiesterase inhibitory activity, which is potentially useful in the treatment of asthma.
The
reaction
of
2-((2-(2-aminobenzylamino)ethylamino)methyl)benzenamine
with
2hydroxybenzaldehyde give the quinazoline ligand of 2-(3-(4-(2-(2-hydroxyphenyl)-1,2dihydroquinazolin-3(4H)-yl)butyl)-1,2,3,4-tetrahydroquinazolin-2-yl)phenol (L). Treatment of L with
one equivalent of Cadmium(II), Zinc(II) and lanthanide(III) ions and in the presence of
triethylamine yield the corresponding Cadmium(II), Zinc(II) and lanthanide(III) complexes in high
yield. The quinazoline complexes have been studied with IR, 1NMR, 13CNMR, Cosy, HMQC
spectroscopies and microanalysis.
Keywords. quinazoline complexes, polyamine, Cadmium(II) complex, , Zinc(II) complex and
Lanthanide(III) complex.
P-84
Synthesis and characterization of four new asymmetric Schiff base complexes derived
from N1-(2-aminoethyl)benzene-1,2-diamine with 2-Pyridinecarboxaldehyde
a
b
R. Azadbakhta,*, R. Golbodaghib, S. Menatic and H. Mehrana
c
Transition metal complexes of Schiff bases derived from asymmetric ligands have generated
considerable interest because of their interesting physico-chemical properties and potentially useful
catalectic activities. Four Schiff base asymmetric macroacyclic complexes were synthesized by using
of N1-(2-aminoethyl) benzene-1,2-diaminepolyamine with 2-Pyridinecarboxaldehyde in the presence
of Cadmium(II), Nickel(II), Copper(II) and Lanthanide(III) ions. The complexes have been studied
by various spectroscopes (IR and microanalysis). The Schiff base asymmetric macroacyclic
Cadmium (II) and Lanthanide (III) complexes have also been studied with 1HNMR and 13CNMR
spectroscopes.
Keywords: Asymmetric macroacyclic ligand, Schiff base complexes, polyamine, Cadmium(II)
complex, Nickel(II) complex, Copper(II)complex and Lanthanide(III) complex
IICC12
75
P-85
Synthesis and characterization of three new Bis-quinazolines complexes derived from
2-((2-(2-aminobenzylamino)ethylamino)methyl)benzenamine and 2-hydroxy-3methoxybenzaldehyde
a
b
R. Azadbakhta,*, R. Golbodaghib, S. Menatic and M. Khodabandeha
c
The many and varied biological properties of quinazolines have been widely studied in recent years
due to their wide range of chemotherapeutic activities including antiviral, antibacterial, antifungal,
antimalarial, antitumorals, antihypertensive, diuretic, inhibitors of cyclin-dependent kinases,
anticonvulsant, ghrelin receptor antagonists, anti-inflammatory, analgesic and COX-II inhibitors.
The reaction of 2-((2-(2-aminobenzylamino)ethylamino)methyl)benzenamine with 2-hydroxy-3methoxybenzaldehyde give the quinazoline ligand of 2-(3-(2-(2-(2-hydroxy-3-methoxyphenyl)-1,2dihydroquinazolin-3(4H)-yl)ethyl)-1,2,3,4-tetrahydroquinazolin-2-yl)-6-methoxyphenol
(L).
The
complexes of L with Cadmium(II), Zinc(II) and lanthanide(III) ions were synthesized. The
quinazoline complexes have been studied with IR, 1NMR, 13CNMR, Cosy, HMQC spectroscopies and
microanalysis.
Keywords. quinazoline complexes, polyamine, Cadmium(II) complex, , Zinc(II) complex and
Lanthanide(III) complex
P-86
Synthesis and Characterization of binuclear vanadyl Schiff base Complexes
Zahra Azhandeh and Ali Hossein Kianfar*
Salen complexes of transition metals have been used in solution as biomimetic catalysts for oxygen
atom transfer.Vanadium complexes are very interesting as model compounds for the clarification of
several biochemical processes. In this work the binuclear tetradentate (N2O2)2 Schiff base ligands
were synthesized by condensation of 3,3́ diaminobenzydine and salysilaldehyde (1:4 mol ratio) in
methanol. The vanadyl complexes were synthesized via reaction of vanadyl acetylacetonate and the
synthesized ligands in methanol. The ligands and complexes were characterized by IR, UV-Vis, and
elemental analysis. The IR and electronic spectra of binuclear ligands were very similar to the
salophen [bis(salysilaldehyde)phenylenediimmine]. The vibration of azomethine group of the free
ligands was observed at 1600-1630 cm-1. For the synthesized complexes this band was shifted to
the lower frequencies, indicating that the nitrogen atom of the azomethine group is coordinated to
vanadyl. The complexes also show an absorption band at about 950-1000cm-1 that related to V=O
vibrational frequency. The electronic spectra of the complexes show the interligand charge transfer
of the Schiff bases. The d-d transition of the synthesized complexes was appeared in the visible
region as two distinct absorptions and show that the environment of the metal ions is different. This
property was seen in the NMR spectra of the Schiff base ligands.
Keywords: binuclear Schiff base complexes, Vanadyl Schiff base complexes
76
IICC12
P-87
Crystal Engineering in the Crystal Packing of Mercury (II) Halides of N-phenyl-2pyrazine carboxamide Ligand
A. Azhdari Tehrani, B. Mir Mohammad Sadegh and H.R Khavasi*
Department of Chemistry, University of Shahid Beheshti, Tehran, Iran
The field of crystal engineering has been driven by the desire to rationally design technologically
useful materials. As this area has developed, certain strategies have been widely exploited, most
notably hydrogen-bonding and metal coordination, although other, somewhat weaker interactions
are also recognized as useful tools. These weaker interactions include donor-acceptor interactions
as well as the donor-acceptor π-stacking of electron-rich and electron-poor planar aromatics. In this
report, we focus on crystal engineering of Mercury (II) Halides N-phenyl-2-pyrazine carboxamide.
The Results show that the N-phenyl-2-pyrazine carboxamide Ligand contains structural features
that can engage in three modes of intermolecular interactions: (1) metal-ligand coordination, (2)
hydrogen bonding, and (3) π-π stacking.
Key Words: crystal Engineering, weak interactions, carboxamide
P-88
Synthesis, characterization ,antibacterial properties studies Cr-Phthalocyanine
a
M. Azimia, G. Geimachya, Sh.Ghammamy *, b Kh Mehrania and F. Shabania
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Ardabil, Iran,
young researchers club (Ardabil branch.) Iran
b
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Ghazvin,Iran
E-mail: [email protected] or [email protected]
Phthalocyanine complexes (Pcs) are a class of compounds with two-dimensional delocalized π–
electron system and metal-N bonds [1-2]. To be OL materials, the Pcs have some advantages for
optical limiting, such as chemical stability and diversity of chemical variations. The architectural
flexibility of Pcs facilitates the tuning of photophysical and optical properties over a very broad
range by changing the peripheral substituents and the central metal ion of the macrocycle. To
overcome the low solubility, peripheral substitutions were investigated to make Pcs soluble in a
variety of solvents. The Cr-phthalocyanine was obtained by the reaction (reaction (1)) and
characterized. The molecular structure is shown in FIG 1. The chains strongly suppress aggregation
and greatly improve solubility. The characterization of the compounds was accomplished by IR and
UV-VIS spectral data. The biological and oxidative properties of this phthalocyanine specially
antibacterial effect were studied on a number of type of bacteries.
Keywords: Cr-Phthalocyanine, IR, UV-VIS, antibacterial properties, oxidative properties
IICC12
77
P-89
Syntheses of new triazene ligand, 1-(2-ethoxy phenyl), 3-(4-nitro phenyl)triazene, and
solution studies of two types of Cu(I) salts with 1-(2-ethoxy phenyl)3-(4-nitro
phenyl)triazene
a
a
M.K Rofouei , aSalameh Azimi*
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
In recent years, the self-assembled metal–organic complexes have attracted intense attention
because of their fascinating molecular structures and crystal-packing motif, and the organic ligands
play an important role in adjusting the architectures of their metal complexes. The reaction of 1-(2ethoxy phenyl)3-(4-nitro phenyl)triazene, [HL], with CuCH3COO and CuCl in acetonitrile as solvent,
resulted in the formation of [CuL2] (1) and [CuL] (2), respectively. These compounds were
characterized by means of NMR, FT-IR, UV spectroscopy and CHN analysis. In a typical procedure,
the absorbance of 2.0 ml of ligand was measured by UV spectrophotometer. Then a known amount
of the concentrated solution of cupper (I) acetate or cupper chloride solution was added in a
stepwise manner using a 5µl Hamilton syringe. The mole ratio data obtained by the
physicochemical method employed were fitted by using a non-linear least-squares curve fitting
program KINFIT. The resulting absorbance against [Cu+]/[HL] mole ratio plot, reveals distinct
inflection points at a metal-to-ligand molar ratio of about 2 and 1 emphasizing the formation of a
1:2 and 1:1 complexes. The conditional formation constants were evaluated as log K = 5.25 ±
0.003 and log K =5.46 ± 0.001 for compounds 1 and 2, respectively.
Keywords: Triazene; Cupper (I) acetate, Cupper (I) chloride, Mole ratio
P-90
Mg(BF4)2 doped in the ionic liquid [BMIM][BF4] has efficiently catalyzed the synthesis of
Xanthenes
a
S. C. Azimia, K. Rad-Moghadama,*
Ionic liquids (ILs) are now well known as salts with melting points below 100 ˚C, and typically have
broad liquid ranges, low vapor pressures, and may be both noncoordinating, but highly polar.
Xanthene derivatives are parent compounds of a large number of naturally occurring, as well as
synthetic derivatives, and occupy a prominent position in medicinal chemistry. Therefore, many
alternative catalysts, such as p-toluenesolfonic acid, p-dodecylbenzenesulphonic acid, InCl3/ionic
liquid, Fe3+-montmorilonite , NaHSO4–SiO2 or silica chloride, amberlyst-15, montmorilonite, and
silica sulfuric acid have been reported for the synthesis of xanthenedione derivatives. However,
some of them often involve the use of expensive reagents, hazard organic solvents, and tedious
workup. Herein we studied the reaction between 5,5-dimethyl-1,3- cyclohexanedione (1) and
several aromatic aldehydes in presence of [Bmim][BF4]- 0.5 mol% Mg(BF4)2 at 80 ˚C (Figure 1). In
all cases the reaction gives the products in good yields and prevents problems which mainly
associate with using solvents such as cost, handling, safety and pollution. In conclusion, we have
developed a novel and efficient method for the synthesis of 1,8-dioxo-octahydroxanthenes in high
yields by employing a novel ionic liquid which is inexpensive, easily available, and reusable such
that make this method simple, clean, practical and economically viable.
Keywords: 1,8-Dioxo-octahydroxanthenes, Ionic liquid, Solvent free, Reusable Catalyst
78
IICC12
P-91
Synthesis and Characterization of pentacoordinate Cobalt (III) Complexes with
Unsymmetrical N2OS Coordination Spheres
a
L. Azimiana, Sh. Esmaielzadehb*
Department of Chemistry, Islamic Azad University, Firozabad branch, Iran
b
Department of Chemistry, Islamic Azad University, Darab branch, Iran
[email protected]
Symmetric tetradentate Schiff base complexes have been used extensively as macrocycle models,
while unsymmetric complexes are very important in biological systems and in industrial catalysis.
Many cobalt(III) tertiary phosphine complexes have been suggested as models for the vitamin B12.
The properties of these complexes were examined with the aim of gaining an in sight into the
chemistry of the related biological molecules. Some new pentacoordinate tertiary phosphine
complexes of the types [Co(cdacacen)(PBu3)]ClO4.H2O, [Co(cdacPhen)(PBu3)]ClO4.H2O and
[Co(cdaccF3en)(PBu3)]ClO4.H2O
(where
cdacacen
({methyl-2-[N-[2(acetonate)ethylidynenitrilo]ethyl}aminato(-1)-1-cyclo-pentenedithiocarboxylate, cdacPhen {methyl2-[N-[2-(acetonate)phenylidynenitrilo]ethyl}aminato(-1)-1-cyclopentene-dithiocarboxylate,
cdaccF3en
{methyl-2-[N-[2-(acetonate)triflourolidynenitrilo]ethyl}amiato(-1)-1cyclopentenedithiocarbo-xylate) have been prepared and characterized with 1HNMR, IR, UV-Vis and
elemental analysis method.
Keywords: Tertiary phosphine complexes, Pentacoordinate, Ligands, Synthesis.
P-92
A 3D macrocyclic ligand as the excellent receptor for encapsulation of fluoride anion: a
Gas Phase Theoretical Study
Elmira Azizi,a Mahdi Rezaei Sameti,a , Mehdi Bayatb, Sadegh Salehzadeh*,b
Department of Chemistry, Faculty of Science, Malayer University ,Malayer, Iran
Faculty of Chemistry, Bu-Ali-Sina University, Hamedan, Iran (e-mail: [email protected])
a
b
Significant efforts have been made to elucidate the structural aspects of anion coordination in
recent years as the coordination chemistry of anions has proven its role in biological systems,
environmental issues, and in the area of medicine and catalysis. Recently Park and Simmons have
been established that azamacropolycycles upon protonation can become good hosts for halides Also
the potentiometric studies on L (1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane,) indicated
that the tiny cryptand was highly selective for fluoride, attributed to the small size of the cryptand
cavity, which was thought to eliminate other anions from entering. Herein we want to report a
theoretical study on binding energy of a series of homolog halides(F, Cl and Br) with L. All
calculations were performed at DFT(B3LYP) level of theory using 3-21G* basis set. The LanL2dz
basis set was added for Cl and Br anions. The result showed that the interaction energy between
the ligand (L) as a receptor and F-, Cl-, and Br- as guests are 594.31, 455.45 and 451.67 kcalmol-1.
Although the the binding energies of chloride and bromide anions are comparable the entering of
the bromide anion into the L has been never reported. On the other hand, the amount of
interaction energy of L with fuolride anion is considerably great, indicating that it is a good receptor
for this anion. Thus the result of our theoretical study on binding energies in these complexes
supports the recent published mechanism for transformation of chloride with fluoride anion from
the cavity of macrocyclic ligands.
Keywords: Macrocyclic ligands, Theoretical study, Anion receptor.
IICC12
79
P-93
Fe3O4 Nanoparticles as Magnetically Recoverable Catalyst for Friedel–Crafts Acylation
Reaction in Solvent-Free Condition
Mahboobeh Azizi, Hasan Nasrabadi, S. Jafar Hoseini*, Alireza Salimi Beni
[email protected]
Department of chemistry,Faculty of sience,yasouj university,yasouj,iran
Fe3O4 nanoparticles have attracted worldwide attention due to many biological and technological
applications. Application of Fe3O4 nanoparticles without any modification as catalyst in organic
reactions is very rare. These magnetic nanoparticles can be separated easily by external magnetic
field . This strategy is simple, economical and promising for industrial applications. Synthesis of
Fe3O4 nanoparticles was performed at a pH = 10-11, with a stoichiometric ratio of 2:1 (Fe3+/Fe2+) in
a non-oxidizing oxygen environment. These nanoparticles were characterized by IR–spectroscopy,
scanning electron microscope (SEM) and X-ray differaction (XRD) method. In this work, we have
showed that Fe3O4 nanoparticles catalyzed Friedel–Crafts acylation of activated and unactivated
aromatic compounds such as anisole and chlorobenzene with acid chlorides in solvent-free
conditions. Easy separation of catalyst, mild reaction conditions, short reaction times, and removing
of solvents are the advantages of this work.
Keywords: Friedel–Crafts, Solvent-Free, Fe3O4 Nanoparticles, Catalyst
P-94
Synthesis and Spectroscopic Studies of Novel Complexes [R2Sn(C4H8S2O2)]2
(R=Me,Bu,Ph) and [R2Si(C4H8S2O2]2 (R=Me)
S.Azizi and A.Tarassoli*
Department of Chemistry, College of Science,Shahid Chamran University, Ahvaz, Iran
A fascinating field of investigation within the general topics of organotin chemistry concerns the
design and synthesis of complexes containing Sn—O and Sn—S bonds. In view of a variety of
diorganotin (ΙV) adducts having oxygen and sulfur ligands are known to show antitumor activity,
the reaction of 2,5-dihydroxy-1,4-dithiane with R2SnCl2 (R=Me ,Bu, Ph) are carried out at different
experimental conditions in an inert atmosphere. The yields of solid products were generally over
70% , and are melted over 300°C(dec). These new complexes were extensively studied by means
of IR spectrophotometry and,1H ,13C and 119Sn nmr spectroscopy. The IR and,1H, 13C nmr studies
are indicated that the proton is eliminated from the OH groups and Sn—O bonds are formed,and
119
Sn nmr shows that the Sn has the coordination number of 4 in these complexes.Therefore, we
suggest the [R2Sn(C4H8S2O2)]2 structure for these new complexes.The reaction of
dimethyldichlorosilane (Me2SiCl2) with 2,5-dihydroxy-1,4-dithiane is also carried out at different
conditions in an inert atmosphere in a similar manner.The new products were characterized by
1
H,13C,29Si nmr spectroscopy as well as IR spectrophotometry.In conclusion, it seems that the 2,5dihydroxy-1,4-dithiane is a very good condidate for the reactions with organotin and organosilicon
halides.
Keywords: Organotin , organosilicon , 2,5-dihydroxy-1,4-dithiane ,
nmr spectroscopy.
119
Sn nmr spectroscopy ,
29
Si
80
IICC12
P-95
Effect of Presence of the New Organic Additives on Crystal Phase and Crystallite Size of
Zirconia Nanoparticles
a
F. Heshmatpour *,a, R. Babadi Aghakhanpour a
Department of chemistry, Faculty of science, K.N.T. University of Technology, Tehran, Iran
The present study has devised the sol gel method using glucose and fructose as two novel organic
additives so as to synthesize zirconia nanoparticles. The presence of these organic additives has
produced some positive effect on the phase transition from tetragonal to monoclinic and played an
important role in the morphology and crystallite size of the nanoparticles. After calcination at 700
°C, the crystal phase and crystallite size of the samples have been determined by X-ray diffraction
(XRD) analysis. In comparison with the sample without organic additives, the sample with organic
additives had more intense tetragonal peaks and lower crystallite size. In fact, the formation rate of
monoclinic phase decreased in the presence of the organic additives and the amount of tetragonal
phase increased. FT-IR spectra have shown Zr-O-Zr bond. Besides, the morphology of the samples
has been investigated by FE-SEM and TEM micrographs. All the analyses consistently have shown
fairly uniform nanoparticles with small size, containing both tetragonal and monoclinic phase with
crystallite size between 10-25 nm.
Keywords: Nanoparticles, Organic Additives, Sol-Gel, Zirconia
P-96
Synthesis of non-crystalline boron powder by thermal reduction method
S. Babaee* and M. A. Zaree
Faculty of Materials, University of Malek Ashtar, Tehran, Iran, P. O. Box. 16765/3454.
Elemental boron powder is used to modify performance characteristics of materials used in
metallurgy, aerospace, and nuclear installations. In this research work, a thermal reduction method
using anhydrous boric acid and magnesium as reactants was used for synthesis of non-crystalline
boron powder. Variables affecting on the preparation process (e.g. kind and ratio of reactants,
reaction medium and temperature) and purification process (e.g. leaching process, furnace
conditions such as temperature, media and preserving time) were evaluated and optimized. After
optimizing of the conditions, the boron with brown color produced and its characteristics such as
crystality, particle size, purity and impurity contents specified with X-ray diffraction (XRD), X-ray
fluorescence (XRF), scanning electron microscope (SEM), particle size analyzer (PSA) and
inductively coupled plasma spectrometry (ICP) techniques. In this manner, amorphous boron (with
98 ± 0.5% purity and average particle size of about 0.5 µm with 90% occurrence frequency),
metallic (0.2± 0.05%) and nonmetallic (1.5± 0.3%) impurities were produced. Finally, the synthetic
powder was successfully applied for some energetic materials and the obtained results were in
satisfactory agreement by those of carried out from standard boron.
Keywords: Boron, Synthetic powder, Purification, Non-crystalline, Thermal reduction method
IICC12
81
P-97
Evaluation of 6-amino-5-cyano-3-methyl-1,4-diphenyl-1,4-dihydropyrano[2,3c]pyrazole as an orally drug in treatment of cadmium toxicity of rats as biological model
M. Babaie*. A. Sh. Saljooghi, S. J. Fatemi, H. Sheibani
The effect of 6-amino-5-cyano-3-methyl-1,4-diphenyl-1,4-dihydropyrano[2,3-c]pyrazole as a
chelating agent on the excretion of cadmium was evaluated in cadmium-poisoned Wistar rats
following food and drink administration. The above chelating agent was prepared in a one step
procedure from a three-component reaction of 3-alkyl-1-phenyl-2-pyrazolin-5-one, aryl aldehydes
and malononitrile in the presence of base catalysts such as sodium acetate and magnesium oxide
(MgO). High surface area MgO as a highly effective heterogeneous base catalyst effectively
catalyzes these reactions. The present research aimed to characterize the potential efficiency of
our presented chelator as an oral drug chelator after cadmium administration for 60 days. This
chelator significantly enhanced the urinary and biliary excretion of cadmium and restored the
altered levels of iron. The chelator was given orally to different groups of rats for a period of one
week immediately after cadmium administration. After chelation therapy, animals were killed by
exsanguinations from abdominal aorta. Blood, kidneys, liver and heart samples were collected and
prepared for determination of cadmium. Cadmium and iron concentrations in various tissues were
determined by graphite furnace and flame atomic absorption spectrometry (GFAAS and FAAS)
methods, respectively. The chelation therapy results showed the present chelator is able to remove
cadmium ions from different tissues while iron concentration return to normal level and clinical
symptoms also reduce.
Keywords: Cadmium toxicity, Chelation therapy, 6-Amino-5-cyano-3-methyl-1,4-diphenyl-1,4dihydropyrano[2,3-c]pyrazole.
P-98
Synthesis and solvatochromism studies of new mixed-chelate dinuclear copper(II)
complexes with different counter ions
E. Rezaee, H. Golchoubian*
Department of Physical-Inorganic chemistry, University of Mazandaran, Babolsar, Iran
Mixed-chelate dinuclear complexes type [Cu2(diamine)2(TAE)]X2, where TAE = tetraacetylethane;
diamine = N,N-dimethyl-N'-benzylethylenediamine (diamine1) or N,N'-dibenylethylenediamine
(diamine2); X = ClO4, BPh4 have been synthesized and characterized on the bases of elemental
analysis, spectroscopic
and conductance measurements. The X-ray crystal analysis of
[Cu2(diamine1)2(TAE)](ClO4)2 demonstrated the expected dinuclear structure and that two
copper(II) ions are not equivalent as shown below. The solvatochromism of the complexes were
investigated in various organic solvents and also compared with those of corresponding
mononuclear complexes [Cu(diamine)(acac)]ClO4. Their solvatochromism were also investigated
with different solvent parameters models using stepwise multiple linear regression (SMLR) method.
The results suggested that the DN parameter of solvent has the dominate contribution to the shift
of the d-d absorption band of the complexes. The results demonstrated that the complexes with
counter ions of BPh4 are more solvatochromic in very weak donor solvents owing to their
disinclination in ion-pair formation. The cations [Cu2(diamine)2(TAE)]2+ decompose in very strong
donor solvents on heating but are stable at room temperature over several hours.
Keywords: Mixed-chelate; Copper(II) complex; Solvatochromism; Dinuclear complex;
Tetraacetylethane; Diamine, SMLR, X-ray crystallography.
82
IICC12
P-99
The synthesis and characterization of Zn-Al layered double hydroxide/ Fe3O4 nano
composites
R. Babazade, Z. Rezvani∗
Department of Chemistry,Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, Iran
Coated magnetite Fe3O4 is a promising material due to its wide range of applications in magnetic
fluids, dynamic sealing ,information storage , medicine , lithium-iron batteries , and catalysis. In this
research work , a core–shell structured magnetic layered inorganic– inorganic material involving
Zn/Al layered double hydroxides (LDHs) and Iron oxide (Fe3O4 ) nano particles is assembled by a
co-precipitation method. The powder X-ray diffraction patterns show the strong and sharp peaks for
the Zn/Al - LDHs and weak peaks for magnetic Fe3O4.Layered double hydroxides (LDHs) of the
type [Zn1-x Alx(OH)2]x+[(Cl-)x.mH2O] with variable Zn/Al molar ratios prepared Zn/Al/Cl LDH with
Zn/Al molar ratio of 4 were synthesized by co-precipitation method at various pH , then Zn-Al
layered double hydroxide/ Fe3O4 nano composites have benn prepared by co-precipitation method
with Zn/Fe3O4 molar ratio of 2 and 4 .The best pH for synthesis of Zn/Al-Fe3O4 nanocomposite was
between 7.5 - 8. In this pH the X-ray peaks were sharper and didn’t show the impurity peaks. The
particle size of Fe3O4 and nanocomposite have been studied by SEM.
Keywords: Zn/ Al LDH, Fe3O4 , nanocomposite, coprecipitation
P-100
Photocatalytic inactivation of E. coli using SnO2-ZnO Nanocomposite Film
Elahe Badria, Nasrin Talebianab,*, Monir Dodibc
Department of Chemistry, Faculty of Science, Islamic Azad University, Shahreza branch, I.R.
Iran
In the present study, SnO2-ZnO nanocomposite thin films with different molar ratio were
successfully prepared by the sol–gel method on glass substrates for antibacterial applications. The
structure and surface properties of the films were characterized by X-ray diffraction (XRD) and
scanning electron microscopy (SEM). Escherichia coli (E. coli, ATCC 25922) was selected as a model
for the Gram-negative bacteria. The bactericidal activity for the above bacteria cells was estimated
by relative number of bacteria survived calculated from the number of viable cells which form
colonies on the nutrient agar plates. The influence of the SnO2-ZnO nanocomposite composition on
the structural features and the antibacterial properties of the thin films are reported and discussed.
The coatings exhibited a high antibacterial activity, which was enhanced with the increase of Zn/Sn
ratio.
Keywords: Zinc oxide; Nanocomposite; Photocatalyst; Sol–gel method; Antibacterial.
IICC12
83
P-101
Synthesis and Characterization of Fe3+, Cr3+ and Mn2+ Complexes with Three Dentate N
and O Donor Schiff-Base Ligand
S.Baghbania,B.Shaabanib*,E.Nikjooc,R.Shafiee zadehc,M.Khansoltanic,F.Khosravic,E.Faraj
zadehc,N.Haji zadehc
a
Department of Chemistry, Islamic Azad University Ardabil Branch, Ardabil, Iran
b
c
The chemistry of Schiff bases, driven from the condensation reaction of primary amines with
carbonyl compounds, aldehydes and ketones, is an area of increasing interest. Metal complexes
with these ligands have numerous applications, such as, in the treatment of cancer, as
antibactericide agents, as antivirus agents, as fungicide agents and for other biological properties.
In this work we have synthesized three dentate Schiff-base ligand from the reaction of 3-hydroxy-2naphthohydrazied with 2-hyroxy-3-methoxy benzaldehyde and its complexes with Fe3+, Cr3+ and
Mn2+ cations. The complexes were characterized with IR, Uv/Vis and conductance measurements.
Increasing of the concentration of complexes causes an increase in their anticancer activities.
Comparison of spectroscopic results for the ligand and complexes also conductometric data and
visible absorption spectra for complexes suggest that ligand act as a three dentate and coordinate
via two oxygen and immine nitrogen.
Keywords: Schiff-base, Transition metal cations, Complex
P-102
Synthesis and structure of chromium complexes with new Tetradentate Schiff base
N2O2-Type ligand.
R. R. khojasteh*, M.Bagheri, K.Yavangi.
Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.
Email : ma.bagheri64 @yahoo.com
The chemistry of Schiff base is an area of increasing interest. Metal complexes with these bases
have numerous applications, such as, in the treatment of cancer, antibactericide, antivirus agents,
and other properties. In this research two chromium(III) and (VI) complexes of Tetradentate Schiff
bases have been prepared by condensing of salicylaldehyde with 4-methyl 1,2-phenylenediamine.
These were characterized by elemental analysis, IR, molarconductivity and NMR. The free ligand
were also characterized by 1H, 13C NMR spectra. The 13C NMR and IR spectra of the free ligand
and the complexes are compared and discussed.
Keyword : Tetradentate Schiff base, Chromium(VI), Salicylaldehyde, 4-methyl 1,2phenylenediamine.
84
IICC12
P-103
Palladium and copper complexes with Oxygen-Nitrogen Mixed Donors as Efficient
Catalysts for the Heck Reaction
a
M. Bagherzadeha*, M. Aminia
The Mizoroki-Heck reaction has become one of the most useful carbon-carbon bond-forming
reactions in organic synthesis and therefore the Heck reaction has been intensively developed from
synthetic and mechanistic points of view, as articulated by the impressive number of reviews and
book chapters. Two novel complexes of Pd(II) and Cu(II) with a simple bidentate ligand, 2-(2'hydroxyphenyl)-5,6-dihydro-1,3-oxazine have been prepared and the molecular structures of these
complexes have been confirmed by X-ray structure analysis, NMR, IR and UV-Visible spectroscopy.
The catalytic behavior of these two complexes was investigated in the Heck reaction. The results
show that these complexes efficiently catalyze the Heck reaction of aryl halides with olefins at 120
ºC in 8 h. The procedure is simple and efficient for coupling various aryl halides with olefins and
does not involve an induction period.
Keywords: Oxazine ligand; Palladium; Copper; Heck reaction
P-104
Synthesis, Spectroscopic Characterization and Thermal Analysis of Ni2+, Cu2+ and Zn2+
Complexes with a Schiff Base Ligand: 6-Methoxy-2-{[(5-chloro-2hydroxyphenyl)imino]methyl}phenol
a
M. Bagherzalakia,*, T. Sedaghatb, M. Kootib
Department of Chemistry, Science and Research Branch, Islamic Azad University of Khouzestan,
Ahvaz, Iran
b
Department of Chemistry, Shahid Chamran University, Ahvaz, Iran
The research field dealing with Schiff base metal complexes is very broad due in part to their
potential interest for a number of interdisciplinary areas that include bioinorganic chemistry,
catalysis and magnetochemistry. In the area of bioinorganic chemistry the interest in the Schiff
base complexes lies in that they provide synthetic models for the metal containing sites in
metalloproteins and enzymes. Also they show biological activities including antibacterial, antifungal,
anticancer and herbicidal. In view of the important role of Schiff bases in development of
coordination chemistry, in this research work a Schiff base, 6-methoxy-2-{[(5-chloro-2hydroxyphenyl)imino]methyl}phenol (H2L), has been prepared from reaction of 4-chloro-2aminophenol with 3-methoxysalicylaldehyde. Then the complexes [NiL(H2O)], [CuL(H2O)] and
[ZnL(H2O)] have been synthesized from reaction of H2L with acetate salts of Ni2+, Cu2+ and Zn2+.
These complexes have been characterized by UV-Vis, IR and 1H NMR spectroscopy. Stoichiometry
and thermal behavior of complexes were investigated by thermogravimetry. On the basis of these
data, Schiff base acts as tridentate dianionic ligand and coordinates to the metal via two phenolic
oxygens and one imine nitrogen. Coordination sphere of complexes have been completed by one
molecule of water.
Keywords: Schiff base, Thermogravimetry, Thermal analysis, Spectroscopy
IICC12
85
P-105
Burning of a Cotton Fabric Impregnated by Synthetic Zinc Carbonate Hydroxide as a
Flame Retardant
a
O.Baghia*, S.M. Mostasharia, and M.A.Zanjanchia,
Zinc carbonate hydroxide (ZnCO3.Zn(OH)2) synthesized by means of the multiplebath method was
deposited onto a cotton fabric, and its uniformity was ensured by means of squeeze rolls. Prolonged
burning was observed on treated specimens:200.5 sec for 20.20% of ZnCO3.Zn(OH)2 added to
100g of a dry fabric increased to 337.5 sec for a 45.39% addition.The ashes of the treated
specimens were subjected to X-ray diffraction analysis, and the result was compared with data for
zinc and zinc-oxide powders.The existence of zinc oxide was detected in the ashes,but no traces of
the metallic zinc were discovered. Therefore, it can plausibly be assumed that a reduction –
oxidation reaction occurs during the smoldering process.
Key words :Zinc Carbonate Hydroxide, Flammability, Smoldering.
P-106
Three-component Hosomi-Sakurai Reactions Catalyzed by heteropolyacids
M.J. Bagi, R. Fazaeli* and H. Aliyan
Allylsilane is one of the most useful functional groups for carbon-carbon bond forming reactions.
Allylsilanes can be conventionally prepared and reacted with aldehyde, ketone, enone and other
electrophiles in the presence of Lewis acid. However, protodesilylation sometimes occurs as an
undesirable side reaction in Lewis acid promoted carbon-carbon bond formation reactions. In recent
decades, uses of heteropoly acids (HPAs) as catalysts for fine organic synthetic processes have
been developed and are important for industries related with fine chemicals, including flavors,
pharmaceuticals and food industries. A simple and versatile method for Hosomi-Sakurai three
component coupling reaction via condensation of aldehydes, silyl ethers (or corresponding alcohols)
and allylsilanes in the presence of catalytic amount of H4SiW12O40 was described. The reaction
proceeds efficiently under ambient conditions with good to excellent yields.
Keywords: heteropoly acids (HPAs), polyoxometalates (POMs), Hosomi-Sakurai, three component
coupling.
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P-107
Self-assembly of Platinum Nanoparticles at the Toluene - Water Interface
a
M. Bahramia, S. J. Hoseinia,*, M. Rashidib
Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj, 74831, Iran
[email protected]
b
Department of Chemistry, Faculty of Sciences, Shiraz University, Shiraz, 71454, Iran
Self-assembly of nanoparticles at the interface between two immiscible liquids is a potentially
alternative approach to fabricate a particle monolayer in regular two dimensional array. Platinum is
a noble and expensive metal with high catalytic activity and stability that has many technological
applications. Catalytic efficiency and selectivity of platinum are highly dependent on the size and
shape of the platinum material. Therefore, many researches into the design of novel platinum and
platinum based nanomaterials are in progress. The reaction occurs at the two immiscible liquids
giving rise to a film at the interface. This simple technique has been shown to yield nanocrystals of
metals such as Au, Ag, Pd and Cu. In according to the best of our knowledge, there is no report on
similar procedure for the synthesis of platinum nanoparticles. In this work we have synthesized Pt
nanoparticles from reduction of PtCl2(SMe2)2 as toluene-soluble precursor in the presence of PVP as
capping agent . These nanoparticles were characterized by scanning electron microscopy (SEM), Xray diffraction (XRD) and IR spectroscopy. These nanoparticles showed high catalytic activity in
reduction of the p-nitrophenol to p-aminophenol in the presence of NaBH4.
Keywords: Platinum, Platinum Nanoparticles, Liquid Interface, Self Assembly
P-108
[Mn(salpr)Cl] supported on modified polystyrene as a selective heterogeneous catalyst
for oxidation of olefins
L. Ansari, B. Bahramian*,E.Solimani
Faculty of Chemistry, Shahrood University of Technology, Shahrood, Iran
*
The manganese (III) salen complexes anchored on tailor-made polymers were more
enantioselective without any mass transfer limitation for alkenes on polymer supports. The metal
complexes were also anchored on other supports, but polymeric supports provided better control on
efficiency of catalysts due to microenvironment provided by polymer chains for the substrates in
comparison to zeolites and silica. The metal complexes on solid supports are immobilized either
physically or by forming a covalent bond between metal complexes and supports. But the recovery
of physically linked catalysts has been found to be low in comparison to covalently bound catalysts
due to the leaching of catalysts. This work describes the development of catalytic systems based on
a chloromethylated polystyrene support modified with pentadentate Schiff base bis(salicylidenimino3-propyl)-amine[H2salpr], [Mn(salpr)-PSP], by covalent bond interaction. The heterogeneous
Mn(salpr) catalyst was characterized by FTIR, UV-Vis, SEM. Catalytic activity and reusability of
catalyst in the heterogeneous epoxidation of alkenes were also assessed. The effect of reaction
parameters such as solvent and oxidant in the epoxidation of cis-cyclooctene were also
investigated. We demonstrated that supported manganese salpr catalyst are featured by: (i) easy
preparation and handling of the catalyst and commercially available of support; (ii) higher catalyst
activity in comparison with the homogeneous analogue.
Keywords: heterogeneous, epoxidation, Schiff base
IICC12
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P-109
Highly efficient Epoxidation of alkenes in the presence of sodium periodate using a
novel heterogeneous manganese catalyst
M.EStiri, B. Bahramian*, M.Mirzaei
*
Transition metal complexes of Ti(IV), Mo(VI), Mn(III), Cr(VI) and Fe(III) with polymer-supported
Schiff bases (N2O2 donor set) have been shown to be active catalysts for epoxidation of olefinic
compounds in the presence of hydrogen peroxide, PhIO, tert.-butyl ydroperoxide, NaOCl etc. as
oxidants. The polymeric ligands containing tetradentate N,O donor((H2-DHA-dien)sites were treated
with a solution of manganese(III) acetate to form the metal complex on the support. This
immobilized Mn(III) complex was characterized by elemental analysis, FT-IR, UV–visible diffuse
reflectance, SEM and thermal analysis. The catalytic epoxidation of alkenes were investigated using
the supported catalysts in the presence of sodium periodate as the terminal oxidant. The effect of
various reaction parameters as well as some aspects of catalyst recycling and possible mechanistic
pathways has also been investigated. The heterogeneous catalyst could be reused in further
catalytic reactions for four times with successive increase in cis-cyclooctene conversion and thus, in
initial activity and total turnover number (TON, better than in homogeneous phase reaction). No
metal complex leaching was observed after the catalytic reactions. In conclusion, the Mn(III) Schiff
base complex containing N, O donor ligand acted as an excellent heterogeneous catalyst for
oxidation of various types of alkenes, including cyclic alkenes and primary aliphatic alkenes, to the
corresponding epoxide compounds under mild reaction conditions.
Keywords: Heterogeneous, epoxidation , sodium periodate, Manganese
P-110
Catalytic activity of Mn(III) Schiff base complex containing N, O donor of 3-acetyl-6methyl-2H-pyran-2,4(3H)-dione
M. Estiri, B. Bahramian*, M.Mirzaei
*
In the last decade, Schiff base ligands have received much attention because of their application in
the fields of synthesis and catalysis. This attention is still growing, so that a considerable research
effort is today devoted to the synthesis of new Schiff base complexes with transition metal ions, to
further develop applications in the area of catalysis, material and pharmaceutical chemistry. We
report here the synthesis, characterization and catalytic efficiency of manganese(III) Schiff-base
complex towards olefin oxidation of a variety of alkenes in different solvent media using sodium
periodate as an oxidant. New symmetrical 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione -based Schiff
bases(H2-DHA-dien) has been synthesized. This complex with Mn(III) have been evaluated as
homogeneous catalytic systems for alkene epoxidation with sodium periodate. The effects of
reaction parameters such as solvent, oxidant in the epoxidation of cis-cyclooctene are discussed.
We demonstrated that new manganese (III) Schiff base catalyst are featured by: (i) easy
preparation; (ii) no need of axial ligand in the catalytic system; (iii) high catalyst activity
Keywords: manganese, Schiff base, epoxidation, (H2-DHA-dien)
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IICC12
P-111
Biomimitic oxidation of organic compounds using novel homogeneous pentadentate
Schiff base Mn(III)
L. Ansari, B. Bahramian*, E.Solimani
*
The Schiff base compounds constitute an important class of ligands which have been extensively
studied in coordination chemistry mainly due to their facile synthesis and easily tunable steric,
electronic and catalytic properties. They are also useful in constructing supramolecular structures.
In this work, olefin epoxidation was performed with sodium periodate in the presence manganese
schiff base bis(salicylidenimino-3-propyl)-amine[H2salpr] complex in MeCN at room temperature.
Optimization of this catalyst system was achieved by examining various amounts of the catalyst,
sodium periodate and cyclooctane in different solvents. The effect of different solvents was studied
in the epoxidation of cyclooctene and CH3CN/H2O was chosen as solvent. The effect of the oxygen
donors such as NaIO4, Bu4NIO4, KHSO5, H2O2, H2O2/urea, NaOCl and tert-BuOOH was also studied
in the epoxidation of cyclooctene where NaIO4 was selected as an oxygen donor. Easy preparation,
mild reaction condition, high yields of the products, short reaction time, high selectivity and
inexpensive system make this catalytic system a useful method for oxidizing of alkenes.
Keywords: H2salpr, manganese, Schiff base, epoxidation
P-112
Synthesis and Characterization of Adducts of Ni (II) Schiff base Complexes and DDq
Masomeh Bahramian, Morteza Dostani, Elahe Abiri and Ali Hossein Kianfar*
The interaction and adduct formation of TCNE and TCNQ with Metal Schiff base complexes was
studied well. In the other hand there is no evidence for interaction of DDq
(dichlorodicyanobenzoquinone) and this type of complexes. So in this work the synthesis and
spectral characterization of adducts of salen-type nickel (II) complexes with DDq were investigated.
The salen [bis(salicylaldehyde)ethylenediimmine] Schiff bases and their Ni(II) complexes were
synthesized in methanol. The adducts, [NiL(ddq)] (where L = Salen and its derivative), were
synthesized by reaction of Ni(II) complexes and DDq in chloroform. Adducts were characterized by
IR, UV-Vis, and elemental analysis. The IR spectrum of adducts shows some new bands in the
range of 2220-2240 cm-1 and 1640-1700 cm-1 related to C N and C=O functional groups of DDq.
The electronic spectra of the Ni(II) complexes in solution consist of relatively intense bands in 250400 nm region involving π
π* transition. The electronic spectrum of DDq shows an intense band
in 380 nm. Adduct formation results in some significant changes of the spectra taken place in the
UV-vis region, indicating that the Ni(II) complexes were interacted to DDq. The elemental analysis
are in good agreement with those calculated for the proposed formula of 1:1 Ni(II)L and DDq.
Keywords: Adduct Compounds, DDq, Ni(II) Schiff Base Complexes
IICC12
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P-113
Synthesis and Characterization of Ni(II) NOS Schiff base complexes
Masomeh Bahramian and Ali Hossein Kianfar*,
Some Schiff base compounds have recently been reported as effective corrosion inhibitors for mild
steel, aluminum, copper, and zinc in acid media. Due to the presence of the C=N group, Schiff
bases should be good corrosion inhibitors. In this work some of tridentate (NOS) Schiff base ligands
and their Ni(II) comlexes were investigated. The Schiff base ligands were synthesized by
condensation of 2-aminothiophenol and salicylaldehyde derivatives in methanol. The NiL(O2H)
where (L = tridentate Schiff base ligand) complexes were synthesized via reaction of Ni(II) and
Schiff base ligands in methanol. The NiL(amin) were synthesized by mixing of NiL(O2H) with
appropriate amounts of amine (benzylamine, imidazol, morfoline, pipyridine, pyrolidine) in
methanol. The synthesized ligands and complexes were characterized by IR, UV-Vis and elemental
analysis. The vibration of azomethine group of the free ligands is observed at 1610-1615 cm-1. For
the synthesized complexes this band was shifted to the lower frequencies, indicating that the
nitrogen atom of the azomethine group is coordinated to Ni(II). The N-H vibration shows that the
amines were coordinated to the aqua complexes. The electronic spectra of the aqua and amine
complexes show that the Schiff bases and amines were coordinated to the Ni(II) metal ion. The
elemental analysis is in good agreement with those calculated for the proposed formula of
synthesized complexes.
Keywords: Ni(II) Complexes, Schiff Base Ligands,
P-114
Supramolecular self-assembled cuban like water-bromide clusters stabilized by a
pyridylphosphine iron(II) complex
a
A. Bakhodaa, N. Safaria,*, A. Nemati Kharatb and H. R. Khavasia
Chemistry Department, Shahid Beheshti University,G.C. Evin, Tehran 1983963113, Iran
b
School of Chemistry, University college of Science, University of Tehran, Tehran, Iran
a
Tris(2-pyridyl)phosphine (P(2-py)3) reacts with FeBr3 in 1:1 molar ratio to form dark red crystals
with the empirical formula, { [Fe(PO(2-py)3)2][ (2Br-)(6H2O)] }. In this complex, Fe(II) ion shows an
octahedral geometry. Water molecules present in association with bromide anions to form discrete
Cubes which form an intricate arrays of hydrogen bonding interactions with bromide (Br-) anions
and oxygen atom of water, leading to a hydrogen bonded 3D framework structure. The waterbromide cluster were explored by using X-ray crystal structural determination
Keywords: Tris(2-pyridyl)phosphine; Water cluster; hydrogen bonding; X-ray crystallography
90
IICC12
P-115
Synthesis and Characterization of New Molecular Complexation between SiCl4 and FreeBase Meso-tetraphenylporphyrins
S. Bakhshayesh, H. Dehghani*
Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
Porphyrins and metalloporphyrins fulfill a very important role in the metabolism of living organism
through biological pigments or biochromes. They can be used as photosensitizing drugs in
photodynamic therapy when coupled to the unprotected peptide, DNA, etc. Some metalloporphyrins
are used as therapeutic drugs to correct the disorder of heme metabolism and suppress tumors.
Magnetic resonance imaging of porphyrins and metalloporphyrins is the important characteristic
often used in biomedical field, especially in the treatment of cancer. To date, several porphyrins
with non-planer ring have been synthesized and studied. Porphyrin macrocycles are very flexible
and by introducing substituents selectively at the β- or meso-positions, the properties can be tuned
at will for each specific application. In this study, free-base tetraphenylporphyrin(H2TPP) and
several derivatives, H2T(X)PP (X=3-CH3, 3-OCH3, 4-CH3, 4-OCH3, 4-Cl, 4-CH(CH3)2) were prepared
according to the method of Gonsalves et al. Molecular complexes have been synthesized by reaction
in mild condition between porphyrins and silicon(IV) chloride. The electronic and spectral
characterization of complexes has been performed. IR, 1H NMR, 13C NMR, UV-Vis data of these
compound show that porphyrins as electron donor and SiCl4 as electron accepter give 2:1 adduct.
SiCl4 + 2H2T(X)PP
[SiCl4 (H2T(X)PP)2]
Keywords: Porphyrin, Molecular Complex, Silicon tetrachloride, Electron donor, Electron acceptor.
P-116
Metal Aromaticity in the Cage Compounds consisting of Group 14 Elements
M. Baleghi , S. Soheili, and H. Fallah-Bagher-Shaidaei*
Department of Chemistry, Islamic Azad University-Rasht Branch, P. O. Box 41335-3516, Rasht, Iran.
The concept of aromaticity has been applied usefully to heterocyclic organic compounds, but it is
only beginning to gain acceptance in connection with metallacycles [1]. The cage systems
consisting of Group 14 elements heavier than carbon, i.e., Si, Ge etc. have always been among the
most attractive synthetic challenges in the chemistry, due to their very unusual structural properties
and high reactivity. Therefore, of interest will be to study the stability of each cage skeleton by
replacing alternating CH units by different elements. In this research ab initio and density functional
computations have been used to characterize the aromaticity of group 14 cage compounds. Ring
strain is the most unique feature of these systems because of the tremendous amount of bond
angle distortion needed to close the cage. Our study shows that substitution of heavier elements for
carbon typically reduces the aromaticity of a cage molecule.
Keywords: Metal Aromaticity, Cage Compound, Group 14 Elements, Ab initio
IICC12
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P-117
Synthesis and characterization of three novel binuclear copper (II) complexes with
amine ligands
a
Iran Bamerya*, Hassan Mansouri- Torshizia and Ali Akbar Sabouryb
Department of Chemistry, University of Sistan and Baluchestan, Zahedan, Iran
(*E-mail: [email protected])
b
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran
Copper plays a key role in diverse biological oxidation–reduction reactions. Tyrosinase is the least
known member of the type III copper enzymes and its function is the catalysis of the oxidation of
phenols to their correspondent o-quinones and thus are great interest for different biotechnological
applications. Several binuclear copper chelating complexes have shown to act as model compounds
of the enzyme active site. In the present work we prepared three binuclear copper complexes of
the type [ (trien) Cu (µ-diam) Cu (trien) ] (NO3)4, ( where trien is threiethylentetraamine and µdiam is 1,4-diaminobutane, 1,6- diaminohexane and 1,8-diaminooctane ). These complexes have
been synthesized by reaction of copper nitrate with trien and subsequent addition of bridging
diamine. These complexes have been characterized by the chemical analysis, conductivity
measurements, ultraviolet-visible, infrared and 1H NMR spectroscopy. The infrared spectral studies
of these complexes have ascertained the modes of binding of the dien and diamine ligands to
copper centers. The molar conductance values of these copper complexes in conductivity water
suggest them to be 1:3 electrolytes. Studies of catalytic properties of these complexes in
comparison with tyrosinase are in progress.
Keywords: Copper(II), Tyrosinase, threiethylentetraamine, Active site
P-118
Preparation , characterization and Vibrational spectra of novel ionic liquid based on
tetralkylammonium cation Ionic Liquids with the Mixed Anion: (R)4N[BF2X] (X=F, Cl,
Br)
T. Banibairamia,*, Sh. Ghammami b, G. Geimachya and M. Hajighahramania
a,*
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, , Ardebil,
Iran, young researchers club (Ardabil branch.) Iran . (e-mail: t_ [email protected] )
b
Department of Chemistry, Faculty of Science, Imam Khomeini International University Qazvin,
Iran. E-mail: [email protected] or [email protected]
Ionic liquids are liquids composed entirely of cations and anions within a wide temperature range
(including room temperature). Due to their unique characteristics such as negligible volatility, nonflammability and high thermal stability, they have attracted considerable interest in recent years for
applications as promising “green” electrolytes for electrochemical devices, such as lithium-ion
batteries, dye-sensitized solar cells and super capacitors. Our research aims at exploring
relationship between physical-chemical properties of ionic liquids, the structure and component of
related cations or anions, to develop new synthetic technique and to prepare new ionic liquids with
special properties. In this paper, we will report the preparation of the new ionic liquids comprising
BF3Br mixed ligand anion (Heteroleptic)and different tetra alkylammonium,RN4(R=panthyl, hgzyl,
hepthyl) cations by the straight forward precipitation method and their characterization by
elemental analysis, IR , 1H, 13 C, 81Br and 19F -NMR techniques. Electronic structure calculations for
[BF3Br]¯ anion are calculated at the B3LYP/6-311G level of theory.
Keywords: molten salts, mixed anion, tetra alkylammonium , 81Br –NMR, solvent.
92
IICC12
P-119
Theoretical Studies of Free Energies of Electron Transfer of [SWCNT(5,5)-ArmchairCnH20][La@C72(C6H3Cl2)] (n=20-300) Nanostructure Complexes
Kamran Barkhordari* and Avat Arman Taherpour*
Chemistry Department, Faculty of Science, Islamic Azad University Arak Branch,
P.O. Box 38135-567,, Arak, Iran. [email protected]
[email protected]
It is determined that La@C72 has a non-IPR carbon cage. The addition of a dichlorophenyl radical
on La@C72 leads to La@C72 (C6H3Cl2) (10-12) with a closed shell structure. Endohedral
metallofullerenes of the form La2@C72 have been introduced as an important class of spherical
fullerene groups with unique properties. One of the most recognizable types of carbon nanotubes is
the (5,5) armchair single-walled carbon nanotube. The number of carbon atoms (n) of the SWCNTs
is considered one of the most useful numerical and structural electrochemical properties for
understanding the structural relationship between the structures of the unsaturated molecules
[La@C72 (C6H3Cl2) A-C] (10-12) and [SWCNT(5,5)-armchair-CnH20] (n=20-190) 1-18, to produce
[SWCNT(5,5)-Armchair-CnH20][La@C72(C6H3Cl2)
Non-IPR
Carbon
Cage
A-C]
(n=20-300)
nanostructure complexes. The relationship between this index and the first free energies of electron
transfer (∆Get(1)), as assessed using the electron transfer (ET) equation on the basis of the first
oxidation potentials (oxE1) of A-C for the predicted supramolecular complexes, between 1-18 and
19-29 with endohedral-metallofullerenes A-C as [SWCNT(5,5)-Armchair-CnH20][La@C72(C6H3Cl2)
Non-IPR Carbon Cage A-C] (n=20-300) 37-152, are presented here. The results were extended for
[SWCNT(5,5)-Armchair-CnH20][La@C72(C6H3Cl2) Non-IPR Carbon Cage] (n=20-300) (n=20-300).
Keywords: La2@C72; Single-wall Nanotubes; Free energy of electron transfer; Activated free
energies of electron transfer; Kinetic constant of electron transfer; Marcus Theory.
P-120
Fluorescence of anthracene derivative covalently attached to the nanoporous silica
Roxana Bavand Savadkoohi, Alireza Badiei*, Alireza Abbasi, Taghi Salemnoush
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
[email protected]
The chemical reactivity of the anthracene skeleton allows its modification with a variety of
substituents in the reactive positions 9 and 10. In order to achieve a new fluorescent material,
immobilization of an anthracene derivative into nanoporous silica type LUS-1 functionalized with
amine groups was done. In this work, amino-modified high ordered nanoporous silica type LUS-1
was prepared via the reaction between (3-aminopropyl) triethoxysilane and LUS-1 by the method of
post grafting. An anthracene derivative named 9,10-Bis(chloromethyl)anthracene was synthesized
and immobilized into nano pores of amino-modified LUS-1 in the prescence of triethylamine. There
was evident from the H NMR spectrum that chlorine was substituted in 9, 10 positions of
anthracene. The fluorescent inorganic–organic hybrid material was characterized by XRD, FT-IR, N2Adsorption/Desorption, TGA and SEM techniques and the results demonstrated that the anthracene
derivative was successfully attached into nano channels of the nanoporous LUS-1. The
photoluminescence measurements indicated variations in fluorescent properties of this new hybrid
material while pH of the solution was changed. Therefore this material can behave as a pH probes.
Keywords: Nanoporous Silica, Functionalized, Hybrid materials, Anthracene, Probe.
IICC12
93
P-121
Synthesis and characterization of new trinuclear cobalt complex; [Co3(CH3COO)6(1,5diphenylecarbonohydrazide)2]
Mohammad Saeid Bayati*, Mohammad Erfan Zand
Department chemistry of Islamic Azad University-Firooz Abad- Branch
A new trinuclear cobalt complex[Co3(CH3COO)6(1,5-diphenylecarbonohydrazide)2](1)has been
synthesized and characterized by IR,Uv/Visible and 1HNMR spectroscopy,and melting point.the
structure(1) consist of trinuclear cobalt coordinated by two terminal ligand and six CH3COO-groups
as bridge .the IR spectroscopy exhibit two peaks at 1576cm-1 and 1420cm-1due to asymmetric and
symmetric vibrations COO-of bridging acetate ,respectively .three peaks in 3395cm-1,1651cm-1 and
1290cm-1 observed due to stretching and bending vibration of N-H and C-N vibration ,respectively
.these peaks indicate that 1,5-diphenylecarbonohydrazide exist in our complex. in the Uv/Visible
spectrum observed three absorption in 327nm, 400nm and 663nm.we believe these absorption
occurred because of d d electron transition. In the 1HNMR spectrum observed doublet peaks at
1.9ppm and 2.46ppm due to methyle hydrogens ,quartet peaks at 6.4ppm and 9.87ppm for C-H
groups in acetate bridge, singlet peak in 8.76ppm for N-H and numerous peaks in 7-7.6ppm for
aromatic hydrogens.the complex melting point measured297˚c,that can be indicate in this complex,
chelate ring has been formed .
Keywords: synthesis,trinuclear,cobalt,1,5-diphenylecarbonohydrazide.
P-122
Covalent functionalization of Multi-Wall carbon Nanotubes (MWNTs) by cobalt(II)
Schiff-base complex, Synthesis and characterization
a
Mehdi Bazarganipourb, Masoud Salavati-Niasari a, b, *, Fatemeh Davara
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317–
51167, I. R. Iran.
b
Department of Chemistry, Faculty of Science, University of Kashan, Kashan, P. O. Box. 87317–
51167, I. R. Iran. (E-mail: [email protected])
The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material
science. In the present study, hydroxyl functionalized cobalt(II) Schiff-base has been covalently
anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission
electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis,
UV–Vis, Diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest
that the symmetrical Schiff-base is a bivalent anion with tetradentate N2O2 donors derived from the
phenolic oxygen and azomethine nitrogen. Multi-wall carbon nanotubes covalently anchored
cobalt(II) complex catalyze the oxidation of aliphatic and aromatic alcohols into the corresponding
carboxylic acid analogues and ketones has been carried out using 30% H2O2 in good to high yields.
The reaction is safe, clean and functions in the absence of additives. The system is truly
heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive
runs.
Keywords: Multi-wall carbon nanotubes; Cobalt(II); Heterogeneous catalyst; Oxidation of alcohol.
94
IICC12
P-123
Synthesis, characterization and catalytic activity functionalized Multi-Wall carbon
Nanotubes (MWNTs) by a manganese(III) Schiff base complex
a
Mehdi Bazarganipourb, Masoud Salavati-Niasari a, b, *, Fatemeh Davara
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317–
51167, I. R. Iran.
b
Department of Chemistry, Faculty of Science, University of Kashan, Kashan, P. O. Box. 87317–
51167, I. R. Iran. (E-mail: [email protected])
In the present study, hydroxyl functionalized manganese (III) Schiff-base has been covalently
anchored on modified multi-wall carbon nanotubes (MWNTs). The new modified MWNTs have been
characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray
photoelectron (XPS), thermal analysis, UV–Vis, Diffuse reflectance (DRS), FT-IR spectroscopy and
elemental analysis. The results suggest that the symmetrical Schiff-base is a bivalent anion with
tetradentate N2O2 donors derived from the phenolic oxygen and azomethine nitrogen. Complex of
manganese, grafted on the walls of MWNTs have been investigated as catalysts for the aerobic
oxidation of para-xylene in the absence of added halogen promoters and using tertbutylhydroperoxide (TBHP) as the initiator at low temperatures. The major products include toluic
acid, toluyl aldehyde and toluyl alcohol. The MWNTs-grafted complex did not undergo any color
change during the reaction and could be easily separated and reused many times. In contrast, the
neat complex, while they were active in the first cycle, was completely destroyed during the run
and changed color. They, however, gave lower conversions compared to the grafted catalyst.
Keywords: Multi-wall carbon nanotubes (MWNTs); Manganese(III); Heterogeneous catalyst;
Oxidation of para-xylene.
P-124
The effect of microencapsulation on thermal properties of ammonium perchlorate
particles
M. bazrgari, S. G. Hosseini and A. Eslami*
Faculty of Chemistry, University of Mazandaran, Babolsar, Iran, P. O. Box: 47416-95447
Ammonium perchlorate (AP) is among the most common oxidizing agents that have been used in
various propellants, but is especially labile. Microencapsulation technique deals with the coating of
fine solid particles with polymeric materials to form microscopic capsules of 1–5000 µm in diameter.
The properties of the coated material can be changed through the process. A solvent/non-solvent
precipitation technique has been used to coat ammonium perchlorate (AP) with a copolymer of
hexafluoropropylene and vinylidene fluoride (HFP-VF) based on the coacervation principle. The
thermal behavior of solid samples has been characterized by means of thermogravimetry (TG) and
differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) was utilized to
examine the encapsulated material morphology. The results of these experiments showed that the
decomposition temperature of most stabilized coated ammonium perchlorate is higher than that of
the pure sample.
Keywords: Coating, Solvent/non-solvent, Microencapsulation, Ammonium perchlorate, Thermal
behavior
IICC12
95
P-125
The thermodynamic studies of mesotetraarylporphyrins with ICl
F. Behnoudnia, H. Dehghani*
Porphyrins are a class of naturally occurring macrocyclic compounds, which play a very important
role in the metabolism of living organisms. Porphyrins and their metal complexes have been the
subject of various studies and find application as photosensitizers in photodynamic therapy and
boron neutron capture thertpy, catalysts, sensorsand molecular electronic devices.
Spectrophotometric method was used for the molecular complexation of ICl with para-substituted
meso-tetraarylporphyrins (H2t(4-X)pp; X: OCH3, CH(CH3)2, CH3, H and Cl) in chloroform solution.
The values of the stability constants were estimated for each complex using a nonlinear
optimization of the complex absorbance versus mole ratio data by package KINFIT. The equilibrium
constants and the thermodynamic parameters were measured spectrophotometrically for 1:1
molecular complex formation of meso-tetraarylporphyrins as donors with ICl as acceptor at various
temperatures. The formation constants for the molecular complexes change according to the
following trend: [ICl(H2t(4-OCH3)pp)] > [ICl(H2t(4-CH(CH3)2)pp)] > [ICl(H2t(4-CH3)pp)] >
[ICl(H2tpp)] > ([ICl(H2t(4-Cl)pp)]. Further, the thermodynamic parameters, ∆G0, ∆H0 and ∆S0 of the
complexes were obtained.
ICl + H2t(4-X)pp
[(ICl)H2t(4-X)pp]
Keywords: Porphyrin, Molecular Complex, Iodine (I) chloride, Electron donor, Electron acceptor.
P-126
Synthesis of new Schiff base and its Cu complex
T. Behzadi, F. Ghanbari and N. O. Mahmoodi
The condensation of amines with carbonyl compounds is a venerable useful organic transformation
as the resultant imines are produced. Schiff bases have a chelating structure and are in demand
because they are straightforward to prepare and are moderate electron donors with easily-tunable
electronic and steric effects thus being versatile. Schiff bases constitute an interesting class of
chelating agents capable of coordination metal ions given complex, which serves as models for
biological system. Also these complexes find many important catalytic applications, such as
catalysts for epoxidation of olefins, alkene cyclopropanation, trimethylsilylcyanation of aromatic
aldehydes, borohydride reduction of aromatic ketones, asymmetric oxidation of methyl phenyl
sulfide, application of ion-selective electrodes, determination of heavy metal ions in environment
samples, extraction of metal ions. In contribution, to Schiff base synthesis, we first synthesized the
Schiff base 1 by reaction of terephtalaldehyde with hydrazine hydrate. The next step was synthesis
of the final Schiff base 2 by reaction of synthesized imine 1 by corresponding aldehyde. The
complex was prepared by refluxing of Schiff base 2 with Cu(OAc)2 in ethanol. The spectroscopic
studies of the complex involving IR, Uv-Vis and stoichiometric study shows that Schiff base to Cu
proportion is 1:1.
Keywords: Schiff base, Montmorollonite KSF, Complex, Terephtalaldehyde, Hydrazine hydrate.
96
IICC12
P-127
A DFT Study on the N,N′-Dipyridoxyl (Ethylenediamine) Schiff-Base Ligand and its
Cu(II) Complex
S. Ali Beyramabadi*, Ali Morsali
Department of Chemistry, Faculty of Science, Islamic Azad University, Mashhad branch, Mashhad,
Iran (e-mail: [email protected])
The title Schiff-base ligand (= H2ES) and its Cu(II) salen complex, [Cu(ES)(H2O)], have been
characterized by IR, 1H-NMR, mass spectrometry and elemental analysis. But their x-ray structures
have not been determinated. Theoretical investigation of the IR and NMR spectra is an important
tool for identification of chemical species. Here, all degrees of freedom for the H2ES ligand and Cu
complex geometries were optimized by employing density functional theory (B3LYP functional). At
the same computational level, the optimized geometries were used to compute the IR frequencies
assignments of the ligand and complex together with the 1H-NMR chemical shifts of the ligand. The
optimized geometry of the free ligand is V shape; two pyridine rings are not in the same plane. Its
phenolic protons are engaged in intramolecular hydrogen bonds. Under complexation, the
deprotonated H2ES acts as a dianionic tetradentate ligand in N,N,O-,O- manner, where the
coordinating atoms occupy equatorial positions. The H2O ligand occupies the axial position of the
square-pyramidal complex. The calculated results are consistent with the experimental ones,
confirming suitability of the optimized geometries for the H2ES ligand and its Cu(II) complex.
Keywords: DFT; IR Assignment; NMR; Schiff base; Copper(II), Salen.
P-128
Characterization of 1-Acetylpiperazinyldithiocarbamate and its Transition Metal
Complexes. An ab initio Study
S. Ali Beyramabadi*, Ali Morsali
Department of Chemistry, Faculty of Science, Islamic Azad University, Mashhad branch, Mashhad,
Iran (e-mail: [email protected])
A series of metal complexes of ML2 type have been synthesized (where L = 1acetylpiperazinyldithiocarbamate, M= Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)). The ligand and its
complexes have been characterized by some analysis such as (CHNS), FT-IR, UV–Vis, 1H NMR
spectroscopies and magnetic measurement. Here, full geometry optimizations were carried out by
using density functional theory (B3LYP functional). The calculations showed that chair form of the L
ligand is more stable than boat one. In all the complexes, the anionic ligand acts as a symmetrical
bidentate ligand, via the dithiocarbamato moiety. The Ni(II) and Cu(II) complexe have a square
planar geometry with the center of symmetry, while the Mn(II), Fe(II) and Co(II) complexes have a
distorted-tetrahedral structure. Fully optimized geometries were used to assign the IR frequencies
and to compute the NMR chemical shifts at the same computational level. Calculated results are in
good agreement with the experimental ones, confirming suitability of the proposed and optimized
structures for the L ligand and its complexes.
Keywords: DFT, IR Assignment, NMR, Dithiocarbamate, Square planar, Tetrahedral.
IICC12
97
P-129
Behavior and Partitioning of Organically Modified Montmorillonite (Organoclay) In
Polypropylene/Poly(trimethylen terephthalate) /Nanoclay Blend Nanocomposites Via
Melt Intercalation
a
A.Bigdeli a*,S.Safarib
Department of Textile Engineering, Science and Research Branch, Islamic Azad University, Iran,
([email protected])
b
Faculty of Science, Arak Branch, Islamic Azad University,
Organic/inorganic nano-scaled composites comprise one of the most important classes of synthetic
engineering Materials. Their makeup is such that they can be transformed into new materials
possessing the advantages of both organic materials, such as light-weight, flexibility, good
moldability, inorganic materials, such as high strength, heat stability, and chemical resistance. The
main objective of this work was to study the effect of presence of organically modified
montmorillonite (organoclay) and the compatibilizer (iPPgMA) on morphology development in
PP/PTT/Nanoclay nanocomposites. Nanocomposites of Polypropylene/Poly(trimethylen)
with
C12PPh–MMT as an organoclay were manufactured by melt intercalation process in a twin screw
extruder. The incorporation of inorganic solid particles has been used as a method to stabilize the
blend morphology due to the compatibilization effect produced by the adsorption of the two
polymers on the solid surface. The compatibility of PP/PTT blends can be dramatically improved
with the addition of nanoclay and PP-g-MA, which posse’s excellent effect to reduce interfacial
tension. Selective localization of nanoclay at the interface of immiscible PP/PTT polymer blend can
be achieved by introducing a copolymer that preferentially localizes at the blend interface and has
the highest affinity for nanoclay.
Keywords:Polypropylene,
Poly(trimethylene
Morphology, Melt Intercalation
terephthalate),
Organoclay,
Nanocomposite,
P-130
Synthesis and Characterization of two novel complexes of 2-aminonicotinic acid with
Cu(II) and Zn(II)
K. Bijanzad, A. Tadjarodi*
Department or Chemistry, Iran University of Science and Technology, Tehran, Iran
One attractive class of ligands comprises pyridine ring with versatile nitrogen and oxygen containing
functional groups such as 2-aminonicotinic acid (Hanic). Hanic is a potential chelate through N or O
donor atoms. The topology of the potential donor atoms in Hanic suggests that this ligand can form
supramolecular assemblies. Herein we report the synthesis and characterization of two novel
complexes of Hanic with copper and zinc metals. Straightforward mixing of aqueous solutions of
metal nitrates of copper and zinc with the ligand dissolved in ethanol and neutralized by potassium
hydroxide in molar ratio 1:2:2 gave the desired complexes with the molecular formula of
[Cu(C6H5N2O2)2].3/4H2O and [Zn(C6H5N2O2)2] respectively. Both complexes are characterized by FTIR, UV-Visible and NMR spectroscopic techniques and elemental analysis. The results suggests that
Hanic ligand coordinates through N(of NH2) and O atoms to the metal centers in both of
compounds.
Keywords: 2-aminonicotinic acid, Cu(II) and Zn(II) complexes.
98
IICC12
P-131
Axial Base Dependence of Catalytic Activity in a Series of Partially Brominated mesotetraphenylporphyrins for Oxidation of Organosulfurs with tetra-nbutylammonium oxone: A Comparative Study
a
E. Bohloulbandia, S. Rayatia,*, S. Zakavib,* and P. Jafarzadeha
b
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, 45195-1159 GavaZang, Zanjan, Iran
Since sulfones are valuable synthetic intermediates for the construction of chemically and
biologically important molecules, oxidation of sulfides to sulfoxides and/or sulfones has been the
subject of extensive studies. In the other hand the introduction of both bulky and electronwithdrawing substituents in the β-positions of the porphyrin ring has been commonly explored as a
means to design metalloporphyrins potentially more resistant to oxidative degradation and
catalytically more efficient. In the present research a homologous series of β-brominated porphyrins
derived from meso-tetraphenylporphyrinatomanganese(III) acetate was prepared and investigated
as cytochrome P450 models. The influence of the degree of β-bromination on the UV–Vis spectra,
and the catalytic properties of the metalloporphyrins were examined. In summary, the use of
imidazole (ImH) as co-catalyst and different molar ratio of ImH to catalyst have different effects on
the product selectivity as well as the total conversion in the oxidation of oranosulfurs to the
corrsponding sulfoxides and sulfones with tetra-n-butylammonium oxone in the presence of the title
metalloporphyrins.
Keywords: Porphyrin, Catalyst, Sulfide, Axial base.
P-132
Electronic properties of doped open-ended single-wall carbon nanotubes
a
F. Buazara,*, H. Hamadib
Department of Marine Chemistry, Khoramshahr Marine Science and Technology University,
Khoramshahr, Iran
b
Department of Chemistry, University of Ahwaz, Ahwaz, Iran. (e-mail: [email protected])
We have investigated the electrostatic, charge and properties of four open-ended single-wall carbon
nanotubes (SWNT (18,0)) model clusters: C108H36, C108N36, C108N18B18 and C108P36 in zigzag geometry.
Theoretical calculations were performed by using AM1-RHF semiempirical molecular orbital show
that curved nanotubes can be obtained by the incorporation of such heteroatom. The result shows
that hexagonal rings in the nanotubes not twisted by substitutional foreign atoms just phosphor
atoms slightly change the edge honeycomb structures. The aim of the present treatise is to
computationally address the structural properties, enegetics, HOMO-LUMO energy gaps, total
charge densities and electrostatic potentials of open-ended SWCNT (18, 0) in zigzag form.
Furthermore, the dopants N, P and concurrent N & B SWCNTs are compared with those of pristine
SWCNT. The geometry optimizations of all the structures leading to energy minima are achieved
using AM1 (Austin Model 1) self-consistent fields molecular orbital (SCF MO) method at restricted
Hatree-Fock (RHF) level. in view of the fact that it allows for treatment of reasonably large systems,
the optimizations are obtained by the application of a conjugate gradient method Polak-Ribiere
(convergence limit of 0.0001kcal/mol) and RMS gradient of 0.001 (kcal/Ǻmol).
Keywords: Carbon nanotube; SWCNT; Electronic structure; Semi-empirical; AM1; Open-ended
tubes
IICC12
99
P-133
Impact of starch on Al nanocrystal growth in water medium
a
Khoramshahr, Iran
b
Department of Chemistry, University of Ahwaz, Ahwaz, Iran. (E-mail: [email protected])
Arc synthesis of Al nanoparticles (Al Nps) are compared and contrasted in distilled and tab water
media, making use of a modified anodic discharging plasma method. It is found that better yield
purity, monodispersity and the mean size (20.1 nm), are made by addition of 5% starch, as a
controlling nanocrystal growth parameter, to the distilled water medium, where more spherical Al
Nps are observed, at 50 A/cm2. Due to its long alkyl chain, starch easily dissolves the Al Nps and
prevents their aggregation in distilled water. Morover, the X-ray diffraction (XRD), energy-dispersive
X-ray spectroscopy (EDX), and scanning electron microscopy (SEM) show strong dependence of
nanoparticle size, color, morphology, and composition on the media employed. In tab water, along
with Al Nps (40.9 nm), both nanoalumina (γ-Al2O3, 49.8 nm), and nanobayerite (Al(OH)3, 50.2 nm),
are produced in comparable quantities. Besides ob taining three different nanoproducts, another
key problem in water is the particle agglomerations, or the tendency of the particles to adhere in
small clumps, which makes dispersion and effective use of the nanoparticles much more difficult.
However, the light Al Nps products, are easily separable form the dark oxidized nanopowder (γAl2O3, Al(OH)3). In contrast to our above observations for arc fabrications in tab water, higher yields
of purer, more monodispersed Al Nps, with smaller mean size (10 nm lower in diameter), are
encountered, showing less Al2O3 impurity, in distilled water.
Keywords: Aluminum nanoparticle; Arc discharge; Starch; media; water
P-134
α/β Phase transformations in tungsten nanoparticles arc fabrications
a
Khoramshahr, Iran
b
Department of Chemistry, University of Ahwaz, Ahwaz, Iran
We discussed the fabrication of tungsten nanoparticles (W Nps) using arc discharge as novel
technique. Our research focused on optimizing operation parameters such as applied current and
media environment. The size, morphology and the crystalline phase (α- vs. β-W Nps) are altered by
changing the applied currents (40-160 A/cm2), as well as the employed media (gaseous nitrogen,
open air, distilled water, and ethylene glycol- all free of any surfactant or stabilizer). Gaseous
nitrogen at 100 A provide the best recipe for the arc fabrication of relatively purest, most dispersed,
body-centered cubic (bcc) α-W Nps with rather small average size of 68 nm, determined by TEM,
SEM, and XRD analyses. Regardless of the medium used, mixed α- and β-W Nps are encountered at
lower currents. In contrast, only the stable metallic α-W form is observed, at higher currents (80160 A). Arc discharge is found as a rather convenient, inexpensive, easy and versatile method, for
fabrication of the desired W Nps.
Keywords: Tungsten nanoparticle; Arc discharge; X-ray diffraction; TEM; SEM
100
IICC12
P-135
Synthesis of nanoscale magnesium oxide via sol-gel method
M. Chamacka, Ak. Hosseinianb, A. R. Mahjouba,*
Department of Chemistry, Tarbiat Modares University, 14115-175 Tehran, Iran
Department of Engineering Science, University Colleges of Engineering, University of Tehran, P.O.
Box 11365-4563 Tehran, Iran
a
b
Magnesium oxide (MgO) is an exceptionally important material for its wide applications in catalyst,
toxic waste remediation, refractory material, paint, superconductor products and so on. Recently,
much research has been focused on the fabrication and characterization of MgO nanostructures due
to novel properties superior to their bulk counterparts, as well as promising utilizations in optical
and electronic fields. Therefore, various methods have been developed to prepare novel MgO
nanostructures by using different raw materials or catalysts. However, the morphology and
properties of the resulting MgO differ and depend largely on the synthesis route and processing
conditions. The sol–gel process has assumed a special significance for synthesis nowadays because
it is simple, cost effective, and capable of yielding unique properties (e.g., large surface area-tovolume ratio, narrow particle size distribution, etc.) at relatively low temperatures. Factors such as
temperature, time, pH, catalytic agent for gel formation, and the environmental conditions
drastically affect the characteristics of the final product. In this work magnesium oxide with
diameter about 58 nm, width and length respectively 77 and 330nm are synthesized via sol-gel
method by using magnesium nitrate and oxalic acid as precursors. The final product is characterized
by IR, XRD and SEM.
Keywords: Magnesium oxide, Sol-gel, Nanoparticle, SEM, XRD
P-136
Synthesis, Characterization and Biological Activity of Proton Transferred Gold(III)
Complexes
A. Dabaghi and A. Abedi*
Au(III) complexes are isoelectronic and isostructural with Pt(II) complexes, so they appeared to be
excellent candidates for anticancer evaluation. In the present work, [Hpz(py)4][AuCl4] and
[Hdpyk][AuCl4] complexes were prepared from the reaction of HAuCl4.3H2O with
tetrapyridylpyrazine (pz(py)4) and dipyridylketone (dpyk) in methanol. Both complexes were
characterized by elemental analysis, IR, UV-Vis, 1H NMR, and 13C NMR spectroscopy and their
structures were studied by single-crystal diffraction method. In these complexes, Au(III) ion is fourcoordinated with four chloride ligands in a square-planar environment. The complexes were tested
in four different tumor cell lines HELA, NIH-3T3, JURCAT, HEP2. The Result showed that the
mentioned Au(III) compounds have significant effects on the anti-tumor activity.
Keywords: Gold(III) complex, Tetrapyridylpyrazin, Dipyridylketone, In vitro, Anticancer.
IICC12
101
P-137
Efficient method for the synthesis of amidoalkyl naphthols catalyzed by RuCl3.nH2O as a
homogeneous catalyst
A. Dadashia, K. Tabatabaeiana*, A. Khorshidia, M. Mamaghania
a
In Recent years multi-component reactions (MCRs) have gained much importance in organic
synthesis as they furnish the desired products in a single operation without isolating the
intermediates. Therefore, the design of a novel MCRs have attracted great attention from research
groups working in medicinal chemistry, drug discovery and material science. The multi-component
condensation reaction between arylaldehydes, 2-naphthol and amides in the presence of Lewis acid
catalysts such as iodine, K5CoW12O40.3H2O, p-TSA and sulfamic acid is one of the straightforward
approaches for the synthesis of amidoalkyl naphthols. In spite of potential utility of aforementioned
routes for the synthesis of amidoalkyl naphthols, some of these methods suffer from severe
drawbacks such as unsatisfactory yields, long reaction times and toxic reagents. Thus the
development of a new procedure for the synthesis of amidoalkyl naphthols would be highly
desirable. In this work we have reported a new and effective methodology for the synthesis of
amidoalkyl naphthols by three component coupling of 2-naphthol, aromatic aldehydes and amides
in the presence of Ruthenium chloride hydrate as a homogeneous catalyst.
Keywords: Amidoalkyl naphthol, Ruthenium, Multi-component reaction.
P-138
Ruthenium chloride hydrate catalyzed preparation of unsymmetrical bis(indolyl)alkanes
at room temperature
A. Dadashia, K. Tabatabaeiana*, A. Khorshidia, M. Mamaghania
a
Indole fragment is a key structural element of many biologically active compounds such as
antibacterials, antivirals and anti-inflammatory agents. Many indole derivatives are used as
antibiotics in pharmaceuticals. Among them bis(indolyl)alkanes and their derivatives are found in
bioactive metabolites of terrestrial and marine origin. Thus the synthesis of bis(indolyl)alkane
derivatives currently is of great interest. Various methods have been developed for the synthesis of
BIMs via condensation reaction between aldehydes and indoles in the presence of protic or Lewis
acid is one of the straightforward approaches for the synthesis of bis(indolyl)methanes. Although
the synthesis of symmetrical BIAs has been studied extensively, the synthesis of unsymmetrical
BIAs is still highly sought-after in synthetic community. With the aim to develop more efficient
synthetic processes, we herein describe a practical method for the preparation of unsymmetrical
bis(indolyl)alkane derivatives via condensation reaction between indole and (1H-indole-3yl)(alkyl)methanol in presence of Ruthenium chloride hydrate as a homogeneous catalyst.
Keywords: Indole, Ruthenium, Unsymmetrical bis(indolyl) alkane.
102
IICC12
P-139
Oxidative Addition of MeI to a Binuclear Cyclometalated Organoplatinum(II) Complex
M. Dadkhah Aseman, S.M. Nabavizadeh and M. Rashidi*
Department of Chemistry, University of Shiraz, Shiraz, Iran
The binuclear complex [Pt2Me2(bhq)2(µ-dppf)], 1, in which bhq=benzo [h]quinoline and dppf=1,1′bis(diphenylphosphino)ferrocene, was synthesize by the reaction of [PtMe(SMe2)(bhq)] with 0.5
equiv of dppf at room temperature. The reaction of Pt(II)-Pt(II) complex 1 with excess MeI gave
the Pt(IV)-Pt(IV) complex [Pt2I2Me4(bhq)2(µ-dppf)], 2. All the complexes were fully characterized
using multi nuclear (1H, 31P, 13C, and 195Pt) NMR spectroscopy, and complex 2 was further identified
by X-ray structure determination. The reaction of binuclear Pt(II)-Pt(II) complex 1 with excess MeI
was monitored by low temperature 31P NMR spectroscopy. And the kinetics of the reaction was
studied by UV-Vis spectroscopy. On the basis of data, a mechanism has been suggested for the
reaction which overall involve stepwise oxidation addition of MeI to the two Pt(II) centers. In this
suggested mechanism, the reaction proceeded through a number of Pt(II)-Pt(IV) and Pt(IV)-Pt(IV)
intermediates. Although MeI in each step was trans oxidatively added to one of the Pt(II) centers,
further trans to cis isomerizations of MeI and I groups was also performmed.
Keywords: Cyclometalated complex,1,1΄-bis(diphenylphosphino) ferrocen(dppf)
P-140
Investigation of Reactivity of phosphorus Ylides as Hard Donar Ligands,
with Ag(I), Cd(II), and Pd(II) as Soft Metal Centers. A multinuclear
NMR study
A. R. Dadrass1*,A. SouldoziI2,S. khorsand1 and S. J. Sabunchei3
Chemistry Department ,Urmia University, Urmia 57159-165, Iran
2
Chemistry Department , Urmia Islamic Azad University, Urmia 57159-165, Iran.
3
Faculty of Chemistry, science, Bu-Ali Sina University, Hamadan 65174, Iran
1
The coordination chemistry of ambidentate ligands have been investigated. One of our goals was to
find an ambidentate ligand wherein control of the bonding mode (C vs O). Although many bonding
modes are possible for keto ylies, coordination through ylides methine carbon is more predominant
and observed with soft metal ions, e.g., Pd(II), Pt(II), Hg(II) Au(I), and Au(III), whereas, The ketostabilized ligand can coordinate to a metal center through the ylide,s methine carbon atom (2) or
the carbonyl oxygen atom(3) wherein (R = C6H5, CH3C6H4, R' = H, and R" = BrC6H4). The reaction
between oxophilic group of 3 metal salts and the ambidentate α-keto ylides(4bromobenzoylmethylenetriphenylphosphorane
(BBPPY)
and
(4-bromobenzoylmethylenetriparatolylphosphorane (BBTPPY) in dry methanol and acetonitrile as solvents lead to formation
of C-bound metal-ylide complexes.The aims of our present work are (i) to determine and compare
the molecular structure of the products formed by the title ylides with these kinds of soft metals,
and (ii) to characterize all the products by FT-IR, 1H, 13C and 31P NMR spectroscopic methods and
microanalysis.
Keywords: ligand, phosphorus ylide reaction, phosphorus ylide complexe
IICC12
103
P-141
Chelation of Lead by Combined therapy in rats
Faezeh Dahoee Balooch*, S. Jamil. A. Fatemi,Amir Sh. Saljooghi, Marzieh Iranmanesh, Mohammad
Reza Golbafan
(e-mail:f_dahoee @yahoo.com)
The present research aimed to characterize the potential efficiency of two chelators after Lead
administration for 50 days following two dose levels of 40 and 80 mg/kg body weight daily to male
rats. In this way, two chelators were chosen and tested in the acute rat model. Test 1: In this test,
Deferasirox and Desferrioxamine were given orally and injection to different groups of rats as a
single or combined therapy for the period of one week immediately after Lead administration,
respectively. Test 2: In this test, Desferrioxamine and Deferiprone were given injection and orally to
different groups of rats as a single or combined therapy for the period of one week immediately
after Lead administration, respectively. Test 3: In this test, Deferasirox and Deferiprone were given
orally to different groups of rats as a single or combined therapy for the period of one week
immediately after Lead administration, respectively. Lead and iron concentrations in various tissues
were determined by graphite furnace and flame atomic absorption spectrometry methods
respectively. The combined chelation therapy results show that two chelators are able to remove
Lead ions effective than single therapy.
Key words: Chelation, Desferrioxamine, Deferasirox, Deferiprone, Lead, iron
P-142
Po[0-Clinical evaluation of the effect of Lead on rat organs and investigation of
Deferasirox, Desferrioxamine and Deferiprone as single therapy in treatment of Lead
toxicity
Faezeh Dahoee Balooch*, S. Jamilaldine Fatemi, Amir Shokooh Saljooghi, Marzieh Iranmanesh,
Mohammad Reza Golbafan
The effects of Deferasirox, Desferrioxamine, Deferiprone as chelating agents on the excretion of
Lead was evaluated in Lead-poisoned Wistar rats following feed and drink administration. The
present research aimed to characterize the potential efficiency of these chelators as single therapy
in removing Lead from the body. The evaluation was carried out in poisoned Wistar rats following
food and drink administration for 50 days. Toxic results include as loss of weight, black line on liver
and skin reactions. Desferrioxamine was given as injection, Deferasirox and Deferiprone were given
as orally to different groups of rats for a period of one week immediately after Lead administration,
separately. In each one of tests, Lead and iron concentrations in various tissues were determined
by graphite furnace and flame atomic absorption spectrometry (GFAAS and FAAS) methods,
respectively. The chelation therapy results showed Deferasirox and Deferiprone are able to remove
Lead ions from different tissues especially from heart and kidneys and Desferrioxamine is able to
remove Lead ions from different tissues especially from liver while iron concentration returned to
normal level and clinical symptoms were also reduced.
Keywords: Deferasirox, Desferrioxamine, , deferiprone, Lead toxicity, Chelation therapy, Rats.
104
IICC12
P-143
The antagonism study of potash and various Ammonium sulfate on the flameretardancy imparted to the cotton fabric
Adeleh Hoseini Dalivand*,a, M. Hakimi
Department of Chemistry, Faculty of Sciences, Payame Noor University, Mashhad, Iran
Email:[email protected]
In this investigation, the combination of potash with Ammonium sulfate was found to be effective
for flame–retardancy of a pure cotton fabric, the fabrics were dipped in individual aqueous
suspensions of potash and/or the Ammonium sulfate; meanwhile ,some sets were impregnated with
appropriate admixed solution of both chemicals. The vertical flame spread test was then
accomplished to characterize the flammability of the specimens. An don’t acceptable antagonism
effect was then experienced by using on mixed bath containing potash and Ammonium sulfate
solutions for the impartation of flame – retardancy to a cotton fabric was determined and expressed
by 0/359gr per 100gr fabric.Thermogravimetry (TGA/DTG) of the pure cotton and the treated on
with (cotton+KOH) ,(cotton+ (NH4)2SO4)
and also treated cotton with mixture
{cotton+KOH+(NH4)2 SO4)}were performed and the Thermograms were compared and commented.
The results obtained are in favor of dust or wall effect theory, Gas dilution theory and also catalytic
dehydration theory.
Keywords: flame-retardancy, Antagonism, potash, Ammonium sulfate Thermogravimetry, cotton
fabric.
P-144
31
P NMR Study of the Stoichiometry, Stability and Thermodynamics of New
Complexation between Uranyl (II) Nitrate and Nmethyliminobis(methylenephosphsonic acid) in Two Binary D2O-DMSO-d6 Solvent
Mixtures
Mohsen Irandousta, Hiua Daraeia*, Mohammad Joshaghania, Khodayar Gholivandb, Mohammad B.
Gholivanda (e-mail: [email protected])
a
Chemistry Department, Razi University, Kermanshah, P.O. Box 6714967346, Iran
b
Chemistry Department, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
The
complexation
reaction
between
uranyl
(II)
nitrate,
and
Nmethyliminobis(methylenephosphsonic acid) (MIDPH) was investigated in two different binary
solvents mixtures of D2O-DMSO-d6 at various temperatures using 31P NMR spectroscopy. The
exchange between free ligand and 1:1 complexed ligand was slow on the NMR time scale and two
31
P signals were observed. Formation constant of the resulting complex was evaluated from
integration of two 31P signals. The values of thermodynamic parameters of resulting complex (∆H,
∆S and ∆G) were determined from the temperature dependence of formation constants. In two
solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized. The
NMR spectroscopy has been widely used to study the thermodynamic of complexation reactions.
The chemical shifts, line broadening, and the integral of the signals are quantitative factors used for
these purposes. The versatility of this technique as well as the importance of uranium chemistry,
encouraged us to study the complexation reaction of UO22+ with MIDPH in two binary solvent
mixtures of D2O-DMSO-d6 using 31P NMR spectroscopy.
Keywords: Complexation; Thermodynamic;
methyliminobis(methylenephosphsonic acid).
Formation
constant;
31
P
NMR;
Uranyl;
N-
IICC12
105
P-145
The effect of coordinated metal on rate of nucleophilic substitiution reactions of
pyridinum systems; A computetional study
a
M. Darvishpoura*, S. Jameh-Bozorgia, Z. Javanshira and M. H. Fekrib
Chemistry Department, Science Faculty, Islamic Azad University, Arak Branch, Arak, Iran
b
Chemistry Department, Science Faculty, Islamic Azad University, Khorramabad Branch,
Khorramabad, Iran.
It is now apparent that the application of transition-metal organometalic compounds to the
synthesis of organic molecules is one of the most powerful preparative tools available to the
chemists. The act of coordination alters the electron distribution within the organo group. It is often
of considerable use to be able to carry out specific substituation reactions on ring systems. Many of
these reactions are impossible or difficult to attain by other methods. In this work example of useful
comparative procedure in nucleophilic substitution rate between 4-bromo pyridine involving
coordinated metal and noncordinated by computational Gaussian 03 program package at the HF/6311+G** level have been presented. The Results showed in the nucleophilic substitution reaction of
metalo pyridinum, negative charge can be delocalized onto the metal in the anionic intermediate.
Consequently the intermediate be more stable rather than noncordinated halopyridine. So with
comparison of computed Ea is certained that rate of nucleophilic substitution on ring increase in
presence a metal ion. This matter obtains instrumental method to prepare different derivatives of
pyridine.
Keywords: Nucleophilic substitiution, Pyridine, Organometalic , Ea , HF
P-146
Theoretical studies on formation constants of the Li+ and Na+ complexes of 15-crown5
Faranak Dastineh, Mehdi Bayat, Sadegh Salehzadeh*
Faculty of Chemistry, Bu-Ali-Sina University, Hamedan, Iran
Macrocyclic crown ethers are widely used as a promising separating agent because of their
excellent ability as a neutral host for selective charged metal ions in its narrow cavity in various non
aqueous solvent. The binding ability and selectivity of crown ethers to metal ion depend on several
factors: size of the crown ether cavity, metal ion radius, type of donor atom, conformation, polarity
of the solvent, etc. In this work we introduce a theoretical method for calculation of formation
constants of the Li+ and Na+ complexes of 15-crown-5 in acetone and acetonitrile solutions with
considering following reaction: 15-crown-5(solv) + M(H2O)6 + (solv)
[M(15-crown-5)] + (solv) +
6H2O(solv).The geometry of ligand, corresponding complexes and Li(H2O)6+ and Na(H2O)6+
complexes in the gas phase were optimized at DTF (B3LYP) level of theory using the Gaussian 03
set of programs. All calculations were performed using 6-31G* basis set. The formation constants
were calculated using a general thermodynamic cycle in which the gas phase species are related to
the solvated species. Thus the formation constants of complexes were calculated using by
calculation of the ∆G of the corresponding gas phase reaction and change in the solvation free
energies of species involve in the reaction. The results show that the calculated formations
constants for both studied complexes in both the acetonitrile and acetone solutions are in good
agreement with the reported experimental data.
Keywords: 15-Crown-5, Density functional theory, Formation constants , Solvation free energies
106
IICC12
P-147
A theoretical study on the effect of solvent on formation constants of [Na(15-crown5)]+ complex
Faranak Dastineh, Mehdi Bayat, Sadegh Salehzadeh*
In this work we report a theoretical study on the effect of solvent on formation constants of [Na(15crown-5)]+ complex in different solvents such as CH3OH, CH3CN and CH3COCH3 with considering
two different reactions (eq 1 and 2).
15-crown-5(solv) + Na(H2O)6+(solv)
[Na(15-crown-5)]+(solv) + 6H2O(solv)
(1)
+
15-crown-5·CH3OH(solv) + Na(H2O)6 (solv) + 2CH3OH (solv)
[Na(15-crown-5)]+(solv) + 3H2O
...
(2)
(solv) + 3H2O-CH3OH(solv)
The geometry of all species in the gas phase were optimized at DTF (B3LYP) level of theory using
the Gaussian 03 set of programs. All calculations were performed using 6-31G* basis set. The
formation constants were calculated using a general thermodynamic cycle in which the gas phase
species are related to the solvated species. Thus the formation constants of complexes were
calculated using by calculation of the ∆G of the corresponding gas phase reaction and change in the
solvation free energies of species involve in the reaction. The results show that the calculated
formations constants using equation (1) are in good agreement with the reported experimental data
only in the CH3CN and CH3COCH3 solutions. However, in the case of methanol solution the
calculated formation constants are in good agreement with experimental data only if we consider
the equation (2).
Keywords: Solvent effect, 15-Crown-5, Density functional theory, Formation constants , Solvation
free energies
P-148
Synthesis and characterization of asymmetric diamine and realated Schiff base
complexes with a few metal ions
A. A. Dehghani-Firouzabadia,*
a
The selection of an appropriate ligand for metal complexation can be rationalized by classification of
metals and ligands according to the concept of ‘hard’ and ‘soft’ acids and bases. The presence of
both a hard and a soft donor group in one ligand increases the coordination ability towards hard as
well as soft acidic metals. Schiff bases with donors N, O, S have structural similarities with natural
biological systems and imports in elucidating the mechanism of transformation and racemization
reaction in biological systems due to presence of imine group. Schiff base complexes have been
used as drugs and they possess a wide variety of antimicrobial activity against bacteria, fungi and
certain type of tumors. In this study, we report the preparation of 2-(2-aminoethylthio)aniline and
two new macroacyclic pentadentate (N2O2S) Schiff base ligands by direct condensation of the 2-(2aminoethylthio)aniline with 2-hydroxybenzaldehyde or 4-bromo-2-hydroxybenzaldehyde. Mn(II),
Zn(II). Cd(II), Cu(II) and Ni(II) complexes of these Schiff base ligands have been synthesized.
These compounds characterized by elemental analysis, IR, 1H NMR, 13C NMR and MASS
spectroscopic methods.
Keywords: Asymmetry diamine, Zn(II) complex, Schiff base ligand, pentadentate ligand
IICC12
107
P-149
Synthesis and characterization of a new cadmium(II) macrocyclic Schiff base complex
containing a phenanthrolin
A. A. Dehghani-Firouzabadia,*, H. Keypourb and M. Rezaeivalac
Department of Chemistry, University of Yazd, Yazd, Iran. (e-mail: [email protected])
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 65174, Iran
Department of Chemical Engineering, Hamedan University of Technology, Hamedan 65155, Iran
a
c
The favorable enthalpy for the formation of the metal–ligand bonds overcomes the unfavorable
entropy from the ordering of the multidentate ligand around the metal ion and thereby promotes
the cyclization reaction. The capability of metal ions to promote the template synthesis of
macrocyclic ligands has been studied extensively and depends on several factors related to the
ligand characteristics, as well as on the nature of the metal ion. The stability of macrocyclic metal
complexes depends upon a number of factors, including the number and type of donor atoms
presenting in the ligand and their relative positions within the macrocyclic skeleton, as well as the
number and size of the chelate rings formed on complexation. For transition metal ions, features
such as the nature and magnitude of crystal-field effects play also an important role. Here, we have
used 2,9-dicarboxaldehyde-1,10-phenanthroline as a precursor to achieve cyclocondensation
reaction with 2,2'-(ethane-1,2-diylbis(sulfanediyl))dianiline, and Cd(II) macrocyclic Schiff base
complexe has been prepared by the template reaction. This complex was characterized by
elemental analyses, IR, 1H NMR, 13C NMR and FAB mass spectroscopic methods. The results
indicate that this complex has been synthesis.
Keywords: Phenanthroline, Macrocyclic ligand, Schiff base ligand, Cd(II) complex
P-150
Synthesis and characterization of new heptaaza zinc(II) macrocyclic Schiff base
complex containing two pyridyl unites as pendant arms
c
a
b
There are a number of macrocyclic Schiff base compounds containing one, two, three or four, 2pyridylmethyl pendant arms. We and others have previously reported a one-step synthesis of Schiff
base macrocyclic complexes bearing a primary amino group in the pendant arm via a template
condensation between 2,6-diacetylpyridine and tripodal aliphatic tetraamines. Recently we have
used 2,6-diacetylpyridine, 2,6-diformylpyridine and 2,9-dicarboxaldehyde-1,10-phenanthroline as a
precursor to achieve several kinds of cyclocondensation reactions with a series of multi-amine
derivatives, and a number of pendant arm macrocycles have been prepared in this way.
Here we describe the Zn(II) templated [1+1] cyclocondensation of 2,6-diacetylpyridine with
branched hexadentate amine ligand that producing the complexes containing two 2-methylpyridine
pendant arms. The complex has been characterized by spectroscopic methods such as IR, FAB
mass and elemental analyses.
Keywords: Schiff base ligand, Pendant arm, 2-methylpyridine, macrocyclic ligand
108
IICC12
P-151
Synthesis and characterization of new non-symmetric amine and realated Cd(II) Schiff
base complex
c
a
b
In the area of bioinorganic chemistry the interest in the Schiff base complexes lies in that they
provide synthetic models for the metal-containing sites in metalloproteins and enzymes. A
classification of the Schiff base ligands taking into account their denticity (number of donor atoms)
and type of donor atom set will be made. The majority of the Schiff base ligands comprise N and O
donors, Schiff bases containing mixed donors, i.e., P, S also exist. In this paper for the first time, N(2-(2-aminophenylthio)ethyl)benzene-1,2-diamine is prepared in pure form and its reaction for
Schiff base complex was studied. Then, non-symmetric Cd(II) Schiff base complex was prepared by
reacting a methanolic solution of CdCl2 and 5-bromo-2-hydroxybenzaldehyde with a methanolic
solution of N-(2-(2-aminophenylthio)ethyl)benzene-1,2-diamine. The non-symmetric amine and
Schiff base complex have been characterized by elemental analysis, IR, 1H NMR, 13C NMR and MASS
spectroscopic methods.
Keywords: Schiff base ligand, Non-symmetric amine, Cd(II) complex, N3O2S-donor
P-152
Synthesis and characterization of Aluminum complex withpotasssium oxalate
a
c
b
Leila dehghani , Hoseinali rasekh * , tahere tahmasebi
Department of slamic azad university – firoozabad branch
[email protected]
Aluminum complex K3[Al(C2O4)3] .m H2O with (3<m<4) has been synthesised and
characterization by IR spectroscopy .The structure of K3[Al(C2O4)3] .3H2O consist af Aluminum Al
(III) [Ne] 3d0 has six O atoms. surrounding it .Aluminum complexe is colorless crystals.the
complexes were readily in water,slightly soluble inless polar solvent and insoluble in non- polar
solvent. The crystal structure of K3[Al(C2O4)3] .3H2O consist of discrete Al(C2O4)33-anions
,K+,cation surround each of the K+ atom.the amount of water molecule were identified by
percentage of weight loss. Synthesized K3[Al(C2O4)3] .3H2O .Were found to lose 3H2O .the
therminal decomposition processes of the complexes of K3[Al(C2O4)3] .3H2O occurs in 3 step.
K3[Al(C2O4)3] .3H2O show the typical bidentate coordination mode of the oxalate groups.The IR
data of the synthesised K3[Al(C2O4)3] .3H2O complexes show intense bonds in the range 1700 –
1400 cm-1. Corresponding to C=O stretching .the stretching modes in complexes appear in the
rengions 1400 – 1300 cm-1and 1300 - 1200 cm-1.the frequencies of the M – O stretching mode
occurred in the region 800 – 600 cm-1.the syethesized K3[Al(C2O4)3] .3H2O shows Al–0 stretching
mode at 800 , 720 cm-1.therefore ,comparision of the infrared spectra of monodentate and
bidentate metallic complexs of this ligand will be of considerable interest.the purity of the complex
can be determined by analyzing its constituent (potassium,Aluminum and oxalate)and comparing
the experimental values with the calculated values.
Keywords: Aluminum complexe ,oxalate, bidentate coordination.
IICC12
109
P-153
Molecular Complex Formation between Macrocycle 4´-nitrobenzo-15-crown-5 and
iodine in chloroform and dichloromethane solutions
a
N. Alizadeh a, S. Dehghanikhah
The formation of charge transfer complex between iodine with macrocycle 4´-nitrobenzo-15-crown5 (NB15C5) is investigated spectrophotometrically in chloroform and dichloromethane (DCM)
solutions at 25°C. The observed time dependence of the charge transfer band and subsequent
formation of I3- in solution were related to the slow transformation of the initially formed 1:1
macrocycle.I2 outer complex to an inner electron donor-acceptor(EDA) complex, followed by fast
reaction of the inner complex with iodine to form a triiodine ion. The spectrophotometric results
indicate that gradual release of triiodide ion from its contact ion pair form in the molecular complex
into the solution is the rate determining step of the reaction. The pseudo-first-order rate constants
for the transformation process were evaluated from the absorbance–time data and found to vary in
the order of DCM> CHCl3. The values of the formation constant, Kf , for each complex are evaluated
from Benesi–Hilebrand equation. Stability of the resulting complex in two solvents was also found to
vary in the order of DCM > CHCl3.
Keywords: Charge transfer complex, Spectrophotometry, Kinetic, Crown ether
P-154
Hydrometallurgical process for recovering precious metals from anode slime
H. Dehnamakia, A. Nemati Kharata,*, A. Abdollahib
Department of Chemistry, University of Tehran, Tehran, Iran
b
Fajr Metal Melting Industry, Niroo Battery Manufacturing Company, Tehran, Iran
a
Selection of suitable method for recovery of precious metals from anode slime will be done
according to slime analysis. These methods include pyrometallurgical and Hydrometallurgical
techniques. Since pyrometallurgical methods are done in high temperature, Selenium turns into
volatile SeO2 that causes environmental pollution and reduce recovery of Selenium. In addition,
separation by hyrometallurgical methods can be done with higher efficiency. In the present study a
hydrometallurgical process is used for facile and effective separating of precious metals from anodic
slime. Selenium, Silver and Gold are recovered from the anode slimes of copper electrorefining. The
advantage of this method is that unlike most procedures, without the need for high pressure and
high temperature efficiency is desirable. In this method Arsenic and Antimony, present in anode
slimes selectively and almost quantitatively dissolved in KOH solution. After this extraction, alkaline
roasting of anode slime solubilizes Se. The proposed hydrometallurgical process for Ag and Au
recovery consists of two leaching stages for the extraction of Silver and Gold. Solutions were
analyzed by Inductively Coupled Plasma(ICP).
Keywords: Precious metals, Metallurgical process, Alkaline leaching, Anode slime, Selenium
110
IICC12
P-155
Kinetic Rates of the Fischer Tropsch Synthesis on Co/Ni/Cs/La2O3 Catalyst
F. Dehnavi , A. A. Mirzaei*
chemistry Department, university of sistan & baluchestan, Zahedan, Iran, P. O. Box 98135-674
The Fischer–Tropsch (F–T) synthesis, which produces high-molecular weight hydrocarbon wax from
syngas, is considered an effective solution to the problem of finding suitable substitutes for liquid
fossil fuels. In this present, catalyst has prepared from precursor 80%Co/20%Ni/1%Cs supported
on 90%La2O3 using a dry impregnation method and was calcined at 550 ◦C for 10hr. The kinetics
of Co/Ni/Cs/La2O3 catalyst was studied in a Fixed-bed microreactor. Experimental conditions were
varied as follows: reactor pressure of 2-14 bar, reactor temperatures of 503-543 K, H2/CO feed
ratio of 0.5-1.5, and constant space velocity of 3600 h-1. The CO consumption rate was calculated
by Poly Math software. A number of Langmuir–Hinshelwood–Hougen–Watson type rate equations
were derived on the basis of a detailed set of possible reaction mechanisms originating from the
carbide mechanism for the hydrocarbon formation. 40 models for the Fischer–Tropsch reaction rate
were fitted to the experimental reaction rates. Simulations using the optimal kinetic models derived
showed good agreement both with experimental data and with some kinetic models from literature.
Kewords: Fischer Tropsch synthesis , Co-Ni bimetallic catalyst, Dry impregnation, Kinetics,
Langmuir Hinshelwood model.
P-156
1D-Copper(II) complex [{Cu4(µ-Mesalpn)2(µ1,1,1-N3)2}{Cu(µ1,1-N3)2}]n: Synthesis and
characterization
Multinuclear copper(II) complexes with tetradentate Schiff-base ligands containing hydroxyl group
have attracted more attention owing to their variable structure and properties [1,2]. Polydentate
Schiff-base ligands can act as both bridging and chelating ligands [3,4]. Herein, new 1D-copper(II)
complex [{Cu4(µ-Mesalpn)2(µ1,1,1-N3)2}{Cu(µ1,1-N3)2}]n (1) has been synthesized and characterized
by elemental analyses, FT-IR spectroscopy, variable temperature magnetic measurements and
single-crystal X-ray diffraction. Single crystal X-ray diffraction studies of 1 show that the
coordination environment of the CuII ions in this complex are different.
Keywords: Multinuclear; 1D; Copper(II); Schiff-base; Spectroscopy; Single-crystal
IICC12
111
P-157
1D-Manganese(III) complex [Mn(Brsal-Mepn)(N3)]n: Synthesis and crystal structure
The design and synthesis of transition metal coordination polymers bridged by small conjugated
ligands, such as azido, are cuurently under instense investigation in view of their structure diversity.
Synthesis of new polymeric complexes of manganese (III) have been importance for their
interesting magnetic properties. Herein, 1D-manganese (III) complex [Mn(Brsal-Mepn)(N3)]n (1),
with the symmetrical tetradentate Schiff base ligand Brsal-Mepn and with azide ions has been
synthesized and characterized by elemental analysis and FT-IR spectroscopy. Single crystal X-ray
diffraction studies of 1 show that Mn(III) ion is in a distorted octahedral geometry with an obvious
Jahn-Teller effect, where the tetradentate Schiff base ligand Brsal-Mepn all bind in the equatorial
mode, whereas in the axial direction, the N3- ion acts as an end-to-end bridge in 1.
Keywords: Manganese(III); Schiff-bese; Crystal structure; Octahedral; Jahn-Teller
P-158
1D-Copper(II) complex [Cu4(en)2(µ1,1-N3)4(µ1,1,1-N3)2(µ1,3-N3)2]n: Synthesis and crystal
structure
In the past few years, thousands of azido-metal complexes with diverse azido bridging modes and
different typs of structures such as 1D chains, 2d layesr and 3D networks have been reported.
Herein, 1D-copper(II) complex [Cu4(en)2(µ1,1-N3)4(µ1,1,1-N3)2(µ1,3-N3)2]n (1), with the bidentate ligand
en and with azide ions has been synthesized and characterized by elemental analysis and FT-IR
spectroscopy. Single crystal X-ray diffraction studies of 1 show that Cu(II) ions have different
geometry and are in a distorted octahedral geometry (Cu1 and Cu1i) and in a distorted square
pyramidal geometry (Cu2 and Cu2i).
Keywords: Copper(II); Azide; Crystal structure; Octahedral; Square pyramidal
112
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P-159
1D-Copper(I) complexes with Schiff-base ligand (3,4,5-MeO-ba)2bn: Synthesis and
crystal structures
The azomethines compounds known in the literature as Schiff-bases, having imine groups (-C=N-)
are extensively studied as a bidentate chelating ligand in copper(I) complexes [1,2]. The structure
of copper(I) complexes formed by the reaction of CuX and Schiff-base ligand depende on the
solvent, type of the Schiff-base ligand and X [3,4]. Recent works have focused on the copper(I)
halides systems because they have been successfully used for the synthesis of 1,2 and 3D
coordination polymers [1,2,5,6]. Herein, new 1D-copper(I) complexes [Cu2(µ-(3,4,5-MeO-ba)2bn)(µI)2]n (1) and {Cu2(µ-(3,4-MeO-ba)2en)(µ1,3-NCS)2}n (2) have been prepared. The crystal structures
of 1 and 2 were determined from single-crystal X-ray diffraction analyses and shows the (3,4,5MeO-ba)2en acts as a bridging ligand with the nitrogen atoms of the two imine functions and
leading to the dinuclear [Cu2((µ-(3,4,5-MeO-ba)2en)] groups. In complex 1, dinuclear [Cu2((µ(3,4,5-MeO-ba)2en)] groups are bridged by two iodine anions [(µ-I)2] while in complex 2, the
dinuclear [Cu2((µ-(3,4,5-MeO-ba)2en)] groups are bridged by four thiocyanate anions [(µ-NCS)4] to
form a neutral 1D-copper(I) complexes 1 and 2.
Keywords: Azomethines; Schiff-bese; Crystal structure; Copper(I)
P-160
Synthesis and characterization of new Schiff-base ligand with NO donors and its Cu(II)
and Ni(II) complexes
Aliakbar Dehno Khalajia,*, Sepideh maghsodlou Rada, Gholamhossein Grivanib
b
School of Chemistry, Damghan University, Damghan, P. O. Box 36715-364, Iran
a
A large number of nickel(II) and copper(II) complexes with salicylaldehyde Schiff-base ligands have
been extensively studied for their interesting structural and properties. Asymmetric Schiff-base
ligands have many advantages over their symmetrical counterparts in the composition and
geometry of transition metal complexes and properties. Reported on the synthesis of transition
metal complexes with Schiff-base derived from furfurylamine have been very rare, in this report, an
asymmetric bidentate Schiff-base ligand (5-bromo-2-hydroxybenzyl-2-furylmethyl)imine, (HL), and
their nickel(II) and copper(II) complexes with the general composition ML2 [M = Ni (1) and Cu (2)],
were prepared and characterized by elemental analysis, FT-IR and 1H-NMR spectroscopy (Fig. 1).
The thermal behavior of ligand and complexes was study using thermogravimetry (TG) in order to
evaluate their thermal stability and thermal decomposition pathways. From the FT-IR and and 1HNMR spectra, it was concluded that the ligand is an anionic bidentate NO chelating and is
coordinated to the metal ions through the one azomethine nitrogen atom and one phenolic oxygen
atom. However, the complexes have similar structure, but they have not similar decomposition
steps.
Keywords: Zinc(II); Schiff-bese; diimine; crystal structure; characterization
IICC12
113
P-161
Application of electroactive conductive polymers for uptake of precious metal ions from
aqueous solutions
R. Ansari*, A. F. Delavar
Gold, silver and platinum group metals are considered as the best-known precious metals because
of their uses in art, jewellery and coinage. They could be also very toxic for human and animal
organism and plants and account as the pollutant, since they are extremely toxic to a variety of
aquatic organisms even at trace concentrations and have inhibiting effect upon the activity of many
enzymes. In this research application of some conducting electroactive polymers (polypyrrole,
polyaniline and polythiophene) for uptake of silver ion from aqueous solution has been investigated.
The effect of various experimental parameters on the metal sorption was studied. It was found that
these materials can be applied for uptake of silver ions very effectively under simple open circuit
(electroless) conditions, demonstrating a novel approach for removal/recovery of precious metal
ions such as silver ions from aqueous solutions. The main mechanism for silver removal is
suggested to be a redox process. The finding seems to be very important from economical,
environmental and analytical points of views.
Keywords: Polypyrrole, Polyaniline, Polythiophene, Silver ion, Removal
P-162
Synthesis, Crystal Structure, Spectroscopic, Electrochemical and Antimicrobial
Properties of a Novel Cu(II) Complex with the mixed ligands 2,9-Dimethyl-1,10phenantroline and 4-Hydroxypyridine-2,6-dicarboxylatic acid
Z. Derikvand,*, a G. R. Talei,b H. Aghabozorg,c M. M. Olmstead,d A. Azadbakht,a A. Nematic and J.
Attar Gharamalekic
a
Department of Chemistry, Faculty of Science, Islamic Azad University, Khorramabad Branch,
Khorramabad, Iran, ([email protected])
b
Department of Microbiology, Faculty of Medicine, Lorestan University of Medical Sciences, Razi
Street, Khorramabad 68198, Iran, cFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
d
Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616-5292, USA
A novel mononuclear Cu(II) complex with mixed ligands, (2,9-dimethyl-1,10-phenantroline)(4hydroxypyridine-2,6-dicarboxylato)copper(II) monohydrate, formulated as [Cu(hypydc)(dmp)]·H2O
(hypydc = 4-hydroxypyridine-2,6-dicarboxylate, dmp = 2,9-dimethyl-1,10-phenantroline), was
synthesized and well characterized by single crystal X-ray diffraction analysis, as well as
spectroscopic (IR, UV–Vis), and electrochemical methods. Intermolecular O–H···O and C–H···O
hydrogen bonds, π–π stacking interactions and C–H···π interactions seem to be effective in the
stabilization of the crystal structure. The complex shows two main redox processes that correspond
to the ligand and the metal center reduction. Electrochemical measurements show that the CuII
center is reduced to CuI. The complex was also evaluated for its antimicrobial activity using in vitro
microdilution methods. Six standard bacteria and a strain of Candida albicans were used for the
antimicrobial activities. The preliminary biological assessment suggests that various derivatives of
this new complex can be worthwhile for further antibactrial in vitro and in vivo tests.
Keywords: Cu(II) complex, X-ray structure, Antimicrobial activities, Chelidamic acid.
114
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P-163
Synthesis, characterization and X-ray structure of a new iron(III) complex as a
heterogeneous catalyst in the efficient regioselective synthesis of β-aminoalcohol
under solvent-free conditions
a
Z. Derikvand*,a, Kh. Bakhtiari b and M. Saeedi b
Department of Chemistry, Faculty of Science, Islamic Azad University, Khorramabad Branch,
Khorramabad, Iran
([email protected])
b
Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran
A new mononuclear metal organic complex of Fe(III) containing 4-hydroxypyridine-2,6-dicarboxylic
acid (hypydcH2) and acridine (acr) was synthesized and characterized by elemental analysis, FT-IR,
and single crystal X-ray diffraction. (acrH)[Fe(hypydc)2].4.5H2O (1), has a distorted octahedral
geometry. The dihedral angle between two coordinated (hypydc)2− groups is 83.51Å which shows
that the ligands are almost perpendicular to each other. In 1 acridine is not coordinated to metal
center however in order to balance the charge act as counter cation. In order to investigate the
catalytic activity of this complex, the chemoselective synthesis of β-aminoalcohols was studied in
the presence of this complex as a catalyst. β-Aminoalcohols were obtained in a system containing
this complex, epoxides and aromatic amines high yields under solvent free conditions. Our method
has several advantages including mild reaction conditions, high yields, short reaction times, simple
operation and work-up which make it a useful alternative to existing methods. Additionally, the
protocol does not require volatile and hazardous organic solvents.
Keywords: Iron complex, Crystal structure, Catalytic activities, β-Aminoalcohol, Solvent-free
conditions
P-164
Synthesis and spectral characterization of new binuclear ortho-palladated complexes of
phosphorus ylides and preparation of some derivatives of
[Pd{CHP(C6H4)Ph2COC6H4Me}(µ-Cl)]2
A. Dolatkhah, S. J. Sabounchei*
Faculty of Chemistry, Bu-Ali Sina University, Hamadan 65174, Iran.
Upon reaction of PdCl2 with the ylide Ph3=CHC(O)R in acetonitrile in equimolar ratios at the reflux
temperature gives the dinuclear complexes [Pd{CHP(C6H4)Ph2C(O)R}(µ-Cl)]2, (R= C6H4Cl (1),
C6H4NO2 (2). These complexes are very insoluble in most common solvents neither NMR nor
conductivity studies could be performed. IR absorption bands observed for C=O stretching in these
complexes
indicate
coordination
of
the
ylide
through
carbon.
Complex
[Pd{CHP(C6H4)Ph2COC6H4Me}(µ-Cl)]2 in dichloromethane at the room temperature reacts with dppm
[PPh2CH2PPh2] and dppe [PPh2CH2CH2PPh2] (1:2) to yield the products of bridge-splitting
[Pd{CH{P(C6H4)Ph2C(O)C6H4}Cl(dppm)] (3), and [Pd{CH{P(C6H4)Ph2C(O)C6H4}Cl(dppe)] (4).
These Complexes have been used to prepare new mononuclear palladium derivatives containing
dppm and dppe. The characterization of the compounds was carried out by elemental analysis, IR,
1
H, 31P, and 13C NMR spectroscopy.
Keywords: Phosphorus ylide, Palladium, Orthopalladation, Triphenylphosphine, Dppm, Dppe.
IICC12
115
P-165
Synthesis and Multinuclear NMR study of new mononuclear complexes containing Pd
atom with bifunctionalized ylides and ambidentate ylides
A. Dolatkhah, S. J. Sabounchei* and F. Akhlaghi Bagherjeri
The
chelate
ylide
ligands
[Ph2PCH2CH2PPh2=C(H)C(O)CH2OC(O)CH2CH3]
(Y1)
and
[PPh2CH2PPh2=CHC(O)CH2OC(O)CH2CH3] (Y2) in equimolar ratios using dry dichloromethan as
solvent coordinate to the [PdCl2(COD)] through the ylide carbon and phosphine phosphorus forming
a six or five-membered chelate rings [PdCl2(Y1)] (1) and [PdCl2(Y2)] (2). The reactions of PdCl2
with Ph3P=CHC(O)C6H4Cl (Y3) and Ph3P=CHC(O)C6H4NO2 (Y4) in a 1:2 ratio in dry acetonitrile at
room temperature result the trans complexes [PdCl2(Y3)2] (3) and [PdCl2(Y4)2] (4). IR absorption
bands observed for C=O stretching in these complexes indicate coordination of the ylide through
carbon. The characterization of these compounds was carried out by elemental analysis, IR, 1H, 31P,
and 13C NMR spectroscopy.
Keywords: Phosphorus ylides, Palladium complexes, Cis- trans geometry, Chelate ring.
P-166
Selective Solid-Phase Extraction of Nd(III) from water by Nd(III) Imprinted complex
on Alumina surface
1
A. Ebrahim, M. Manoochehri*
Department of Chemistry, Islamic Azad University-Central Tehran Branch, Tehran, Iran
Neodymium metal dust is a combustion and explosion hazard. Neodymium compounds, as with all
rare earth metals, are of low to moderate toxicity; however its toxicity has not been thoroughly
investigated. Molecular imprinting is a technique to create template-shaped cavities in polymer
matrices with memory of the template molecules to be used in molecular recognition. Molecularly
imprinted materials are prepared using a template molecule and functional monomers that
assemble around the template and subsequently get crosslinked to each other. The functional
monomers, which are self-assembled around the template molecule by interaction between
functional groups on both the template and monomers, are polymerized to form an imprinted
matrix . Then the template molecule is removed from the matrix under certain conditions, leaving
behind a cavity complementary in size and shape to the template. The obtained cavity can work as
a selective binding site for a specific template molecule. A new Nd(III)-imprinted mercaptofunctionalized alumina sorbent was synthesized by an easy one-step reaction by combining a
surface imprinting technique for selective solid phase extraction of trace Nd(III) prior to its
determination by ICP optical emission spectroscopy. The Nd(III)-imprinted sorbent was
characterized by IR spectroscopy. Compared to non-imprinted complex particles, the ion-imprinted
complexes had higher selectivity and adsorption capacity for Nd(III). Optimum condition of Nd(III)
sorption has been investigated.
Keywords: Nd(III) imprinted complex, Surface imprinting technique, Solid phase extraction,
mercapto-functionalized alumina
116
IICC12
P-167
Synthesis and Characterization of a New Inorganic Liquid Acid and Study of its Catalytic
Activity in Esterification Reactions
F. F. Bamoharram a*, M. M. Heravib, M. Roshania , j. Ebrahimia and N. Tavakoli –Hoseinia
a
Department of Chemistry, Islamic Azad University – Mashhad Branch, Mashhad, Iran
b
Department of Chemistry, Alzahra University, Tehran, Iran
Usually for synthesis of ionic liquids (ILs) a Bronsted acid such as sulfuric acid or phosphoric acid
has been used. The principles of green chemistry have been introduced to eliminate or reduce the
use of hazardous materials. It was shown that heteropolyacids in the solid state are green, pure
Bronsted acids and stronger acids than conventional acids. In the present work, we have
synthesized and characterized a new Bronsted acidic IL based on Keggin heteropoly acid and
studied performance and applicability of it as a catalytic medium in the highly selective esterification
of salicylic acid with some aliphatic and benzylic alcohols. The performance of the synthesized IL
was also compared with the known classical catalysts. Our findings showed that the synthesized IL,
catalyzed the esterification reaction and reduced reaction time obviously. The effects of catalyst
structure, concentration, temperature and reaction times have been studied and the optimum
conditions were obtained. In conclusion, for the first time a new and green Bronsted acidic IL based
on Keggin anion were synthesized, and used as effective and green medium for the esterification
reactions. No organic solvent was used, resulting in eco-friendly process.
Keywords: Liquid acid, Heteropolyacid, Catalyst, Esterificarion
P-168
Ruthenium as a homogeneous catalyst for the synthesis of indolo[2,3-a]carbazoles
a
A. Khorshidia,*, K. Tabatabaeiana
The indolocarbazole framework occurs in many alkaloids having diverse biological activities, such as
antitumor, anti-inflammatory and antimicrobial activities. Indolocarbazoles have five different
isomeric forms, amongst them, the [3,2-a]carbazole framework has received the least attention.
Few methods have been reported for the synthesis of this class of compounds, such as double
Fischer indolization of bis(cycloheanone)-m-phenylenedihydrazone or by heating 5aminotetrahydrocarbazole with 2-chlorocyclohexanone. Here, we wish to report a direct synthesis of
indolo[2,3-a]carbazoles from indoles and 1,2-diones, catalyzed be ruthenium (III) as a
homogeneous catalyst.
Keywords: Indolo[2,3-a]carbazoles, Ruthenium, Indole
IICC12
117
P-169
Oxidation of olefins with iodosylbenzene catalyzed by meso-tetra(o-tolyl)
porphyrinatomanganese(III)- and meso-tetra(p-tolyl)porphyrinatomanganese(III)
acetate: a comparative study
a
b
L. Ebrahimia, S. Zakavia,*, S. Rayatib
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 4513766731, Iran (e-mail: [email protected])
The introduction of bulky substituents at ortho-positions of meso-aryl substituents or/and pyrrole βpositions, a part from their electronic properties, gives porphyrins with increased dihedral angles
between the meso-substituted aryls and the porphyrin mean plane such as mesotetramesitylporphyrin (H2tmp) and meso-tetra(2,6-dichlorophenyl)porphyrin (H2tdcpp). [Mntmp]OAc
has been found to show higher catalytic activity relative to Mn(tpp)OAc in the oxidation of sterically
unhindered cycloalkanes and aryalkanes with periodate as oxidant. In a recent work, similar
catalytic activities have been reported for Ru(IV)(tmp)Cl2 and Ru(IV)(tdcpp)Cl2. In the present
work, the catalytic activities of meso-tetra(o-tolyl)porphyrinatomanganese(III) acetate, Mnt(otolyl)p(OAc) and meso-tetra(p-tolyl)porphyrinatomanganese(III) acetate, Mnt(p-tolyl)p(OAc) in
oxidation of different alkenes with iodosylbenzene (PhIO) have been compared. Competitive
oxidation of cis- and trans-stilbene has been used to elucidate the nature of active oxidant. In
summary, the results of this study show that the relative catalytic activity of the metalloporphyrins
cannot be rationalized only by their relative electron-deficiency, so that the sequence of catalytic
activities may change toward different alkenes.
Keywords:
Meso-tetra(o-tolyl)porphyrinatomanganese(III)
acetate,
tolyl)porphyrinatomanganese(III) acetate, Iodosylbenzene, Oxidation of alkenes
Meso-tetra(p-
P-170
Preparation of Fe2O3/Bentonite as a catalyst and determination of optimum condition
for photocatalytic degradation of Acid red 206 dye with taguchi experimental design
method
a
b
M. Ebrahimia*, K. Mahanpoorb,
Department of Chemistry, Islamic Azad University, Arak Branch, Arak,Iran
Department of Chemistry, Islamic Azad University, Arak Branch, Arak,Iran
Heterogeneous photocatalysis has been considered as a cost effective alternative for the
purification of dyecontaining wastewater. Then the photocatalytic decomposition of organic
compounds in wastewater has attracted a great deal of attention .A method of supporting Fe2o3 on
zeolite , without losing the photosesitization of Fe2o3 and the adsorption properties of zeolite ,is
the important aspect while preparing zeolite-Based photocatalysts. A first order reaction with k =
0.035min-1 was observed for the photocatalytic degradation reaction. The effects of some
parameters such as pH , amount of photocatalyst, initial concentration of dye and temperature
were also examined.Results show that Fe2o3/Bentonite is an active photocatalyst for
photodegradation of AR 206 pollutant in water.Based on these results ,a model highlighting the
photogradation activity of immobilized [Fe2o3/Bentonite] which may lead to the developement of
an easy and effective technology in wastewater treatments,is proposed.
Keywords: Photo catalytic, Degradation, Acid red 206(AR206), Zeolite, Taghuchi method.
118
IICC12
P-171
Spectroscopic and thermodynamic studies of charge transfer interactions between a
new water-soluble cobalt (II) Schiff base complex and imidazole derivatives
a
Mehdi ebrahimpoura, Mahdi Behzada,*
Faculty of science, department of chemistry, Semnan University, Semnan, Iran.
Water-soluble cobalt(II) tetradentate Schiff base complexes have been shown to form charge
transfer (CT) complexes with a series of donors including imidazole and 1-methylimidazole. The
investigated water-soluble cobalt(II) Schiff base complex, in this study, is derived from
disodium[bis(5-sulfo-salicylaldehyde)-1,8-Diamino-3,6-dioxaoctan]. The formation constants and
thermodynamic parameters for charge transfer complex formation between water-soluble cobalt(II)
Schiff base complexes and imidazole derivatives were determined by UV-Vis spectroscopy in
aqueous solutions at constant ionic strength (I = 0.2 mol dm−3 KNO3) at pH 7.0 and various
temperatures between 288 and 308 K. all the products were characterized by elemental analysis,
IR, UV-vis,1H NMR spectra.
Keywords: imidazole derivatives; Water-soluble cobalt Schiff base complexes; Charge transfer
complexes; Formation constant; Thermodynamic parameters
P-172
Synthesis and Characterization of Two Organic-Inorganic Hybrids Obtained from
Reaction of Keggin-typPolyoxometallates with 2-Amino-4-methyl pyridine and 2Aminopyrimidine Spacers
Shima Edalatkar Moghadama,*, Hossein Eshtiagh-Hosseinib, Masoud Mirzaeib
Faculty of Chemistry, Islamic Azad University, Shahre rey Tehran Branch, Tehran, Iran
b
Department of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
a
Polyoxometallate constitute a fascinating class of metal-oxygen cluster-compounds with definite size
and shape. They have been found to be extremely versatile inorganic building blocks in view of
their potential applications in catalysis, medicine, theoretical studies, and materials science. Herein,
two new organic-inorganic hybrids Materials based on Polyoxometallate, have been successfully
synthesized and characterized by elemental analyses, IR, NMR spectroscopies. According to the
obtained
results
these
two
hydrated
hybrids
may
be
formulated
as
(2aminopyrimidinium)4(SiO4W12O36) and (2-amino,4-methyl pyridinium)3(PO4W12O36). In these cases,
Keggin anions act as electron accepting species which leading to unique features for synthesized
hybrids.
Keywords: Polyoxometallates;Organic-inorganic hybrid material;2-Amino,4-methyl pyridine;2Aminopyrimidine
IICC12
119
P-173
Synthesis of Novel Organic Compounds by Ruthenium Salt as Homogeneous Catalyst
Via Codensation Reactions
a
b
T. Eftekharia, K. Tabatabaeian*b
Indoles and their derivatives are known to possess various biological properties including
antibacterial, cytotoxic, antioxidative and insecticidal activities, many indole derivatives are used as
antibiotics in pharmaceuticals. There has been tremendous interest to develop highly efficient
transformation for the preparation of organic compounds, as well as biologically active materials,
with potential application in the pharmaceutical or agrochemical industries from the commercially
available compounds. Indole framework is present in many substances commonly found in
nature.Among them, bis(indolyl)methanes (BIMs) are important class of bioactive metabolite. BIM is
effective in the prevention of cancer due to its ability to modulate cancer causing estrogen
metabolites. The scope of this research is synthesis of new bis(indolyl)methanes from the
condensation of various aldehydes and indoles at room temperature in the presence of low
concentration of RuIII catalyst in the short time under very mild conditions,and with good
yields(Scheme 1). All products were confirmed by IR, 1H and 13CNMR spectroscopy.
Keywords: Indole, Ruthenium, Aldehyde, Bis(indolyle)methane.
P-174
Theoretical study of the CO insertion into the Pt-Cp bond of [Pt(Cp)(CO)(X)(PMe3)
Complexes, where X = F, Cl, Br, I
Alireza Ariafarda,b, Zeinab Ejehia*, Shohreh Etaatia, Tahmineh Mehrabia, Azadeh Moradzadeha,Reza
Fazaelic, Maryam Daghighi Aslia
a
Department of Chemistry, Faculty of Science, Central Tehran Branch, Azad University, Shahrak
Gharb, Tehran, Iran (Email:[email protected])
b
c
Deptartment of Chemistry, Faculty of Engineering, South Tehran Branch, Islamic Azad University,
Tehran, Iran
Theoretical chemistry allows chemists to predict materials properties and rates of chemical
processes. Recently Hughes and coworkers experimentally investigated the CO insertion into the PtCp bond starting from [CpPt(CO)I] and in the presence of two equivalents of PMe3. They found that
in the course of reaction two PMe3 are attached to the Pt metal center to form trans[(PMe3)2Pt(CpCO)I] as the final product. We designed two different reaction pathways to investigate
the mechanism of the insertion reaction. The effect of the nature of the spectator ligand X on the
mechanism of the insertion reaction was investigated. Calculations showed that with increasing
electronegativity of X, the insertion barrier decreases while the overall reaction becomes less likely
to happen. For all the X ligands, the most favorable pathway is calculated to be that passing
through a four-center transition state.
120
IICC12
P-175
Synthesis and investigation interactions between N,N'-salicylidenephenylediamine and
Schiff base (salophen) in N,N-dimethyformamide DMF + 1-buthyl-3-methylimidazolium
bromid [BMIm]Br at T = 298.15 K
a
R. Elhamia*, H. Shekaari, A. Bezaatpour, A. soltanpour
Department of Chemistry,University of Mohaghegh Ardabili, Ardabil, Iran.
(e-mail):[email protected]
The condensation of primary amines with carbonyl compounds yields Schiff bases. Chelating ligands
play a central role in the development of the coordination chemistry related to enzymatic reaction,
magnetism, molecular architectures and transition metal catalysts for oligomerization and
polymerization of olefins in both academic and industrial sectors . In this work densities, viscosities,
and refractive indices of the salophen Schiff base in ionic liquid, 1-butyl-3-methylimidazolium
bromide [BMIm]Br + dimethylformamide [DMF] solutions have been measured at 298.15 K. These
data have been used to calculate apparent molar volumes, V , viscosity B-coefficients, for the
mixtures studied. The limiting partial molar volumes, V  , transfer partial molar volumes, ∆trV , and
The viscosity B-coefficients have been determined. It has been observed that values of V , ∆trV 
and viscosity B-coefficients for salophen Schiff base decrease with increasing ionic liquid
concentrations. All these parameters were used to interpret solute-solvent interactions occurring
between the various components in these ternary mixtures. The values of ∆trV  have negative
values for these salophen Schiff base. This indicates the hydrophobic – hydrophobic interactions
between aliphatic groups of salophen Schiff base and ionic liquid.
Keywords: Ionic liquids 1-buthyl - 3-methyl imidazolium bromide . salophen Schiff base . apparent
molar volume . Viscosity, Refractive index
P-176
Synthesis and thermodynamic interactions between N,N'-salicylidenephenylediamine
Schiff base (salophen) in 1-buthyl-3-methylimidazolium bromid [BMIm]Br + N,Ndimethylacetamide DMA solutions at T = 298.15 K
a
R. Elhamia*, H. Shekaari and A. Bezaatpour
In this work densities, viscosities, and refractive indices of the salophen Schiff base in ionic liquid,
1-butyl-3-methylimidazolium bromide [BMIm]Br+dimethylacetamide [DMA] solutions have been
measured at 298.15 K. These data have been used to calculate apparent molar volumes, V ,
viscosity B-coefficients, for the mixtures studied. The limiting partial molar volumes, V  , transfer
partial molar volumes, ∆trV , and The viscosity B-coefficients have been determined. It has been

observed that values of V , ∆trV a
nd viscosity B-coefficients for salophen Schiff base decrease with
increasing ionic liquid concentrations. All these parameters were used to interpret solute-solvent
interactions occurring between the various components in these ternary mixtures. The values of
∆trV  have negative values for these salophen Schiff base. This indicates the hydrophobic –
hydrophobic interactions between aliphatic groups of salophen Schiff base and ionic liquid.
molar volume . viscosity . Refractive index
IICC12
121
P-177
Synthesis and thermodynamic study of N,N'-salicylidenephenylediamine Schiff base
(salophen) in dimethylsolfoxide, (DMSO) + 1-buthyl-3-methylimidazolium bromid
[BMIm]Br at T = 298.15 K
a
R. Elhamia*, H. Shekaari and A. Bezaatpour
In this work densities, viscosities, and refractive indices of the salophen Schiff base in ionic liquid,
1-butyl-3-methylimidazolium bromide [BMIm]Br + dimethyl sulfoxide DMSO solutions have been
measured at 298.15 K. These data have been used to calculate apparent molar volumes, Vφ0,
viscosity B-coefficients, for the mixtures studied. The limiting partial molar volumes, Vφ0 , transfer
partial molar volumes, ∆trVφ0, and The viscosity B-coefficients have been determined. It has been
observed that Vφ0, ∆trVφ0 and B values for salophen Schiff base decrease with increasing ionic liquid
concentrations. All these parameters was used to interpretate solute-solvent interactions occurring
between the various components in these ternary mixtures. The values of ∆trVφ0 have negative
values for these salophen Schiff base. this indicating the hydrophobic – hydrophobic interactions
between aliphatic groups of salophen Schiff base and ionic liquid. Interaction between DMSO an
salophen Schiff base can be display as flow figure.
molar volume . viscosity . Refractive index
P-178
New Vanadium Complexes as Proposed Anticancer Agent
S. M. Emadia, A. Abedia,* and S. N. Ostadb
Department of Toxicology & Pharmacology, University of Tehran Medical Sciences, Iran
a
b
In a systematic effort to identify and develop effective anticancer agent, some vanadium complexes
with nitrogen donor heterocyclic ligands like tetrapyridylpyrazin, di-pyridylketon, neocuprin, and
bipyridin analogues were prepared from the reaction of VCl3 salt with mentioned ligands. The
complexes were characterized by elemental analysis, IR, NMR and UV-Vis spectroscopy. In vitro
evaluation of the complexes as proposed anticancer reagents have been tested in four cancer cell
lines and compared with cis-platin, a well known anticancer drug. Interestingly, in some cases, the
IC50 values of the studied complexes were higher for normal cells but lower against cancer cells in
comparison with Cisplatin.
Keywords: : Vanadium complexes, Heterocyclic ligands, in vitro, Anti cancer agent
122
IICC12
P-179
PZT/TiO2 Photocatalysed degradation of Acid Yellow 36 in aqueous suspentions
Z.Emadian, R.Fazaeli*,M.Yousefi
Department of Chemistry, University of Shahrerey, Tehran, Iran
Department of Chemistry, University of south Tehran, Tehran, Iran
a
c
Lead Zirconate titanate(Pb(Zr0.52Ti0.48)O3)(PZT) nano-powder with a Perovskite structure and
PZT/TiO2 composite photocatalyst were prepared by sol-gel method.These composites were
characterized by powder X-ray diffraction,scanning electron microscopy, and transmission electron
microscopy.The average crystallite diameter of the PZT powder is calculated to be 63 nm. Anatase
type of titanium dioxide(TiO2)powder was used in process. The photocatalysed degradation of Acid
Yellow 36 investigated in aqueous suspensions of PZT/TiO2 under a variety of conditions.The
degradation was studied by monitoring the change in substrate concentration employing UV
spectroscopic analysis technique.The influence of various parameters such as,PH,catalysts,
substrate concentrations, and in the presence of electron acceptor such as hydrogen
peroxide(H2O2)besides molecular oxygen has been investigated.The degradation product Acid
Yellow 36 was analyzed by GC-MS technique.also,the pores of catalysts was evaluated by BJH
technique.
Keywords: PZT/TiO2;Nano-powder;Photocatalysis;Acid Yellow 36;GC-MS;BJH
P-180
Some metal complexes of 2-thiophene aldehyde Thiosemicarbazone: Syntheses,
characterization and X-ray crystal structures of Ni(II) and Co(III) complexes
V. Erfaniyan a, M. Hakimi a,*, R. Takjoob
Department of Chemistry, Payame Noor University (PNU), Mashhad, Iran
Department of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Iran
a
b
Some transition metal complexes CoL3. 2CH3OH, NiL2, CuL2, ZnL2, Zn(HL)Cl2, PdL2, CdL2, Cd(HL)Cl2
and Cd(HL)I2 of SN donor N-(2-hydroxyethyl)-1-(thiophen-2-ylmethylene)hydrazinecarbothioamide
(HL) have been synthesized. Crystal structure of [CoL3]. 2CH3OH (I): The crystal is Trigonal and
with the space group R-3. In [Co(L)3] as a distorted octahedral geometry, the three
thiosemicarbazone bidentate NS ligand in its thiol form (L) is chelating via its N1, S1 donor atoms,
thus forming five membered chelate rings and the thiophene ring is pendant. Crystal structure of
[Ni(L)2] (II): The centrosymmetric structure consists in the neutral molecules [NiL2], with nickel(II)
at the centre of symmetry in P21/n . The coordination environment around the nickel(II) center in II
consists of a square planar fashion of N2S2 donor points. In conclusion: A new series of complexes
were prepared from the novel ligand HL. The spectral data show that the Schiff base exists as a
bidentate ligand by bonding to the metal ion through sulfur and azomethine nitrogen. The
molecular structure of the neutral complexes I and II have been determined by X-ray diffraction
studies as distorted octahedral and square planar, respectively.
Keywords: Thiosemicarbazone, Metal complexes, Crystal structure , Spectroscopy
IICC12
123
P-181
Synthesis and characterization of new acyclic azo-azomethine triazole-based Silver (I)
complex
M. Erfantalab, H. Khanmohammadi*
*
The organic colorants, which usually consisting of azo bands and heterocyclic rings, have been
widely used as dyes owing to their versatility in various fields and high technologies, including
textiles, paper, leather, plastics, lasers, liquid crystalline displays and so on. One particular area of
azo-azomethine chemistry that has been increasing in importance recently involves photophysically
properties and biologically active metal complexes of N, O donor agents. The coordination of metal
ions, especially transition metal ions, to azo-azomethine ligands improves their efficacy and
bioactivity. Furthermore, the structural study of complexes of heterocycle-based azo-azomethine
ligands, especially those containing 1,2,4-triazole moiety, has led to a diverse field of bonding
motifs in the solid state and are further being explored for possible use as novel antimicrobial
agents for wound healing. So, at the present work a new azo-azomethine ligand, H2L, was prepared
by condensation reaction of 3, 5-diamino-1, 2, 4-triazole with azo-coupled salicylaldehyde and was
characterized by elemental analysis, thermal analysis, NMR, IR and UV-vis spectroscopic methods.
The Ag (I) complex of the prepared ligand was also synthesized and characterized.
Key word: Silver complex; TG-DTA; Azo-azomethine; 1, 2, 4-Triazole
P-182
Theoretical investigations on the Hydrogen NMR shielding and vibrational frequencies
of new acyclic 1, 2, 4-triazole-based Schiff base ligand
M. Erfantalab, H. Khanmohammadi*
*
The 1, 2, 4-triazole-based Schiff base ligands are of particular interest because of their electronic
properties and their abilities for complex formation. With this view, it was felt worthwhile to
investigate the electronic structure of 1, 2, 4-triazole-based ligand by employing theoretical
methods. So, in the present work a new 1, 2, 4-triazole-based Schiff base ligand, H4L, was
synthesized and characterized by spectroscopic methods (1H NMR, IR) and elemental analysis.
Density functional theoretical investigation on the structure and vibrational frequencies of H4L was
carried out by using 6-311++G* basis set. Also, nowadays, the GIAO/DFT and CSGT/DFT
approaches are widely used for a variety of heterocyclic-based compounds [3]. Previously, we
showed that GIAO and CSGT calculations with B3LYP/6-31++G* for optimized structure of
pyridazine and pyridine based ligands gave good agreement between experimental and calculated
values of chemical shifts. At this work, the 1H NMR isotopic chemical shielding of gas phase H4L was
systematically studied by the gauge independent atomic orbital (GIAO) and continuous set of gauge
transformation (CSGT) methods at the level of density functional theory (DFT) and the theoretical
vibrational of it was determined and compared with experimental data. The 6-311++G* basis set
was utilized for all of the atoms.
Key words: Schiff base, CSGT, GIAO, NMR, FT-IR, DFT
124
IICC12
P-183
Comparison structure between experimental and theoretical methods of [Cu2(dmptH-2
by computational chemistry
3)(CO3)]
Mohammad Erfan Zand* , Mohammad Saeid Bayati , Asghar Rakeb , Pouria Abbasi , Iman Ghoroori
Department of Chemistry, Islamic Azad University of Firooz Abad-Branch , Firooz Abad, Fars , Iran
Computational chemistry calculates the quantum equation for sub atomic particles. The molecules
form of atoms and atoms form of sub atomic particles such as Electron, Proton and Notron
.Computational chemistry study interaction between this particles. Considering this interactions we
can survey behavior and structure of compounds .Density Functional Theory (DFT), Hartree Fock
(HF) and Moller-Plesset (MP) were branch of computational chemistry methods. Theoretical
chemistry with experimental research helpful for discover the more information of compounds
structure. In the article, [Cu2(dmptH-3)(CO3)]-2 synthesized and characterized by x-ray diffraction
and we used computational chemistry method for obtain information of [Cu2(dmptH-3)(CO3)]-2
complex. So we studied data of length and angle bond of [Cu2(dmptH-3)(CO3)]-2 by computational
chemistry methods (DFT,HF,MP2 ) and compare with experimental data in the abstract reported
DFT method. Calculated geometrical optimized by ( Hartree-Fock ) HF , ( DFT ) B3LYP and ( 2nd
Moller- Plesset ) MP2 methods at LANL2DZ for Cu atoms and 6-31+G* for all atoms standard basis
set .For calculation methods used Gaussian 03W package of program .
Keywords: DFT , HF , MP2 , Computational , Cu complex
P-184
Study Structure and bond [Ni(3TTSC)2] complex by Natural Bond Orbital ( NBO ) and
computational chemistry method
Mohammad Erfan Zand* , Mohammad Saeid Bayati
Department of Chemistry, Islamic Azad University of Firooz Abad - Branch, Firooz Abad , fars , Iran
The [Ni(3TTSC)2] complex synthesized with methanol as solvent. The crystal structure of the
compound has been determined by X-ray diffraction method reported data of length bond angel
this complex. In this paper study compound by Natural Bond Orbital (NBO) and Density Functional
Theory (DFT) computational chemistry method and compare information of theoretical chemistry
and experimental data of structure, reported data of computational method. Density Functional
Method is benefit chemistry theory for [Ni(3TTSC)2] complex . After optimized structure, study
length bond and angel. Calculated DFT by B3LYP method at LANL2DZ for Ni and 6-31+G** for all
atoms standard basis set .We used Natural Bond Orbital (NBO) for study energy bond. For DFT and
NBO calculation used Gaussian 03W package of program.
Keywords: Compare , DFT , NBO , Computation method , Ni complex
IICC12
125
P-185
Computational studies on NN'-(o-phenylene)bis(salicylideneamine): Structure,
Theoritical Characterization and Spectroscopic Properties
Atefeh Ershadi a , Seyed Nezamoddin Mirsattarib,*
Department of chemistry, Islamic Azad University, Shahreza Branch, Shahreza, Iran
b
Department of chemistry, Islamic Azad University, Shahreza Branch, , Shahreza, Iran
([email protected])
a
In
this
paper,
we
report
a
computational
structure
study
on
NN'-(ophenylene)bis(salicylideneamine) [salphH2] ligand. The structure of this ligand was fully optimized
using the most reliable methods (e.g. B3LYP) and at 6-31++G** level. At the same computational
level, the H NMR and C NMR chemical shifts were calculated. Theoretical calculations of harmonic
frequencies at the fully optimized geometries have been performed with B3LYP method and at 631+G** level. Obtained structural parameters are in good agreement with the experimental data
reported for similar compound. The calculation for NBO was done and information about Mullikan
charge, NBO charge and NBO hybridization were obtained. The selected bonds length and angle are
presented. Based on computational methods, intramolecular hydrogen bond could be verified [5].
Calculations demonstrates that nature of hydrogen bonding interactions in salphH2 is to some
extent different than in intramolecular hydrogen bonds without π -electron coupling. The systems
with large π -electron delocalization, like Schiff bases, can be described with the help of resonance
theory.
Keywords: DFT, IR spectra, Mullikan charge, NBO, NMR, Schiff base ligand
P-186
Synthesis and characterization Rh(III) complex with (6,6′ dimethyl-2,2′-bipyridyl)
Esfandiari.Ha* , Jameh-Bozorghib
Department of Chemistry, Azad University - Neyriz Branch
b
Department of Chemistry, Islamic Azad Univercity - Touyserkan Branch
a
2,2′-bipyridine and its derivatives play important roles as molecular scaffolding for supramolecular
assemblies, building block for the synthesis of metallo-dendrimers, thin films of luminescent
complexes and ligand for synthesis of ring-opening metathesis polymerization (ROMP)
monomer.Metal complexes of the type [M(LL)3]n+, where LL iseither 1,10-phenanthroline or a
modified phen ligand, areparticularly attractive species for developing new diagnostic and
therapeutic agents that can recognize and cleave DNA. The ligands or the metal in these complexes
can be varied in an easily controlled manner to facilitate an individual application, thus providing an
easy access for the understanding of details involved in DNA-bindingand cleavage. In this work, it
was synthesized [Rh(phen)2(dmbpy)](PF6)3 complex where, phen= 1,10-phenanthroline and
dmbpy=6,6′ dimethyl-2,2′-bipyridyl and characterized by NMR, IR, UV–Vis spectroscopic technique.
The intense absorption bands at 503 and 568 nm is assigned to ligand field transition for Rh(III)
complex,λ1(1A1g 1T1g), λ 2(1A1g 1T2g). (d
d) by analogy to other Rh(III) polypyridyl
complexes.The visible spectrum is similar to those of the corresponding phen or bpy complexes
except that there is a red shift in the maximum wavelength of absorption. The absorption bands
seen in the UV region are assigned to ligand-centered transitions(π π*).
Keywords: 2,2′-bipyridine, monomer, spectrum, ligand-centered transitions
126
IICC12
P-187
Synthesis of copper sulfide nanoparticles from metal-organic frameworks via
hydrothermal process in the presence of thioglycolic acid
Elaheh Esmaeilia, Masoud Salavati-Niasaria,b,*and Fatemeh Davara
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, Iran.
Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran.
a
b
A thioglycolic acid (TGA)-assisted hydrothermal process has been developed to synthesize copper
sulfide (Cu2S) nanoparticles via the reaction between a new precursor, [Cu(pht)(H2O)]n and
thioglycolic acid. A novel copper coordination polymer [Cu(Pht)(H2O)]n as a precursor was obtained
by chemical precipitation involving an aqueous solution of copper acetate monohydrate and
phthalate anion as a potential O-banded ligand. Fourier transform infrared (FT-IR) results proved
that phthalate anions coordinate to metal cations as a chelating bidentate ligand, making polymeric
structure. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron
microscopy (SEM), UV–vis spectroscopy and Fourier transform infrared (FT-IR) were employed to
characterize the obtained product. TEM images and XRD analysis indicated that the as-synthesized
Cu2S nanopartcles has a crystal phase of hexagonal with a mean size of ~30 nm. Furthermore, the
possible mechanism and the critical factors for the TGA-assisted hydrothermal synthesis of the Cu2S
nanoparticles have been presented. The effect of reactant concentration, mole ratio of TGA to the
Cu2+, temperature and reaction time on the morphology, particle sizes and phase of nanocrystalline
Cu2S products has been investigated.
Keywords: Nanoparticles, Cu2S, Chelating bidentate ligand, Hydrothermal.
P-188
Efficient Adsorption of Heavy Metal Cations on Magnetic Ferrites Nanoparticles
S. Esmaeili and M. Kooti*
Department of Chemistry, Shahid Chamran University, Khozestan, Ahvaz, Iran
( e-mail: [email protected])
In this work we have synthesized a number of nanoscale ferrites, MFe2O4 (M=Co, Ni, Fe, Cu) and
studied their capability for the removal of some heavy metals in low concentration from water. The
required ferrites for this study have been made by either co-precipitation or solid state routes with
some modification. Adsorption studies were performed by adding a certain amount of the ferrite
nanoparticles to an aqueous solution of the heavy metals and for each sample the residual metal
concentration in solution was measured by atomic absorption spectroscopy for different contact
time under constant mechanical stirring. Our study has revealed that these ferrites exhibit different
adsorption ability for the uptake of heavy metal cations. Among the examined ferrites, cobalt ferrite
(CoFe2O4), as magnetic adsorbent, shows the highest adsorption capacity and can be repeatedly
used. Moreover, cobalt ferrite displays different adsorptive tendencies for the studied heavy metals.
The efficiency of cobalt ferrite for the uptake of lead cation from water was more than each of the
other investigated metal cations. The effect of some parameters on the adsorptive efficiency of
CoFe2O4 for heavy metals is under investigation and so far there is no clear order observed between
the types of heavy metal and the tendency of cobalt ferrite for these metals.
Keywords: Ferrites, Nanoparticles, Heavy metals, Adsorption
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127
P-189
Pollutants Removal by Ferrites Nanoparticles
S. Esmaeili and M. Kooti*
(e- mail: [email protected])
We have synthesized a number of nanosized ferrites, including Fe3O4, CoFe2O4, NiFe2O4 and
CuFe2O4 and studied their adsorptive properties for a variety of azo and non-azo dyes. We have
examined the adsorption of methyl orange, alizarin, methylene blue and eriochrome black- T on
three types of ferrites by checking the absorbance of these dyes at their λ max after certain time of
contact with the ferrites. Experiments were performed using a batch equilibrium technique by
placing 0.2 g of ferrite adsorbent in a glass vessel containing 100 mL of a dye solution at
concentrations of about 10-4 M. It was shown that the cobalt ferrite (CoFe2O4), compare with other
ferrites, can act as a superior adsorbent for removing the studied dyes in aqueous solution. The
adsorptive property of cobalt ferrite was also examined for other pollutants, such as phenol,
chromate, thiosulfate and iodide ions. The obtained results clearly showed that cobalt ferrite is able
to remove all these pollutants from water. The chromate ion, however, could not be completely
adsorbed by this ferrite nanoparticle. In most of the experiments of adsorbing of these pollutants,
the used ferrite adsorbent could be regenerated and used repeatedly. The magnetic properties of
cobalt ferrite nanoparticles adsorbents allowed their separation from water by applying a magnetic
field, indicating that cobalt ferrite could be used as a promising and efficient adsorbent for the
removal of various dyes and other potentially toxic pollutants from water.
Keywords: Ferrites, Nanoparticles, Dyes, Pollutants
P-190
Preparation, Physical Characterization, Antibacterial Activity and Thermodynamic
Studies Spectrophotometrically of Ni(II) and Copper(II) Complexes with New Schiff
Base Ligands Giving a NNOS Coordination Sphere
Sh. Esmaielzadeha*, M. Asadib, Kh. Mohammadic and B. Esmaielzadehd
[email protected]
b
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Iran
c
Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr, Iran
d
Faculty Member of Medical, Bushehr University, Bushehr, Iran
a
Some new unsymmetrical tetradentate Schiff base ligands containing a mixed donor set of NNOS
were prepared by the reaction of appropriate Methyl-2-{N-(aminoethane)}amino-1cyclopentenedithiocarboxylate with the appropriate diketons. Their copper(II) and nickel(II)
complexes were synthesized and characterized by IR, 1HNMR, elemental analysis, mass and UV-Vis
techniques. All these Schiff bases and their complexes have also been screened for the antibacterial
(Escherichia coli, Staphylococcus aureus, Streptococcus pyoggenes, Pseudomonas aeruginosa and
Salmonella typhi) by MIC method. Also the thermodynamic formation constants of the complexes of
the prepared ligands with Ni(II) and Cu(II) were determined spectrophotometrically at constant
ionic strength, at 25°C and in DMF solvent. Our results revealed the thermodynamic formation
constant, and the free energy values for Cu(II) complexes are higher than the Ni(II) complexes.
Keyword: Antibacterial, Spectroscopy, Complex, NNOS Coordination, Thermodynamic Studies.
128
IICC12
P-191
Synthesis and characterization of diorganotin(IV) complexes of tetradentate Schiff
bases
Nasim Esmatia,*, Mohammad Yousefia, Alireza Foroumadib
Department of Chemistry, Islamic Azad University, Shahre-Rey Branch, Tehran, Iran
b
Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical
Science, Tehran, Iran
a
A large number of Schiff bases and their complexes are significant interest and attention because of
their biological activity including anti-tumor, antibacterial,and anti-carcinogenic properties.
Organotin(IV) complexes of general formula R2SnCl2L (R=n-Bu, Me) have been prepared from
diorganotin(IV) dichlorides (R2SnCl2) and tetradentate Schiff bases containing N2O2 donor atoms in
the presence of triethylamine. The Schiff bases were derived from salicylaldehyde, acetylacetone
and diamines such as methyl-1,2-phenylenediamine and 2,3-diaminopyridine. The complexes were
characterized by FT-IR, 1H and 119Sn NMR spectra.
The Schiff bases, have been prepared by refluxing the diamines with salicylaldehyde and
acetylacetone, in a 1:2 mole ratio respectively in ethanol. The crude Schiff bases were recrystallized
from ethanol before use. To a solution of appropriate Schiff base ligands in THF and triethylamine
in a 1:2 mole ratio that were stirred continuously, the organotin(IV) dichloride in THF was added
slowly, Finally the mixture was refluxed. After some days, the solvent was evaporated gradually and
crystalline products were obtained. It has been shown that Schiff base complexes derived from this
ligands have strong anticancer activity, e.g., against Ehrlich ascites.
Keywords: Diorganotin(IV) complexes, Schiff bases, NMR spectroscopy
P-192
Synthesis and characterizations of copper(II) complexes containing ONO donor Schiff
base
Roya Esteghamat-Panah and Rasoul Vafazadeh*
Department of Chemistry, Yazd University, Yazd, Iran
(e-mail address: [email protected])
Copper(II) complexes with Schiff base ligands are considerable interest due to their structural and
magnetic properties. In addition, the complexes have been investigated as models for a number of
important biological systems. A new copper(II) complexes have been synthesized with ONO donor
(H2L) Schiff base ligand. The ONO donor ligand was readily synthesized by condensation of
equimolar amounts of salicylaldehyde and aminopropanol in methanol solution. The all complexes,
CuLX, were prepared by reaction equimolar amounts of copper(II) salt, the H2L Schiff base ligand
and X ligand (X= H2O, imidazole, methylimidazole and p-toluidine) in methanol solution. These
copper(II) complexes have been characterized by IR, UV-Vis spectroscopy and elemental analyses.
The IR spectrum of the Schiff base ligand exhibits a strong band at 1640 cm−1 due to υC=N of
imine, which are shifted to lower energies 1621-1615 cm−1 in the spectra of the copper complexes.
The decrease in the frequency indicate a decrease in the C=N bond order due to the coordination
of the azomethine nitrogen to the copper. The fairly broad band of medium intensity appearing at
3285 cm−1 corresponds to the intramolecular hydrogen bonding in the Schiff base ligand, this band
is absent in the complexes.
Keywords: copper(II) complex, tridentate, Schiff base, imidazol, ONO donor
IICC12
129
P-193
Oxidative Addition Chemistry of Monohalo and Dibromoalkanes to
Dimethylplatinum(II) Complexes
B. Z. Momeni∗, S. Etezadi and E. Khozeimeh
Department of Chemistry, K.N. Toosi University of Technology, Iran
The alkyl and aryl platinum(IV) complexes have been considered as the key intermediates in many
important catalytic processes. Dimethylplatinum(II) complexes undergo easy oxidative addition
with different reagents, e.g. alkyl halides and dihaloalkanes leading to stable dimethylplatinum(IV)
complexes. The electron-rich platinum complexes [PtMe2(NN)] {NN = bpy (2,2´- bipyridine), phen
(1,10phenanthroline),
bu2bpy
(4,4´-bis-tert-butyl2,2´-bipyridine)}
reacted
with
diphenylbromomethane to give the corresponding platinum(IV) complexes of cis and trans[PtBrMe2{CH(Ph)2}(NN)] (NN = bpy, phen, bu2bpy). Also, the dimethylplatinum(II) complex of
[PtMe2(bu2bpy)] reacted with a large excess of EtX (X = I, Br) to form dimethylplatinum(IV)
complexes of cis and trans-[PtEtXMe2(bu2bpy)] (X = Br, I). Interestingly, the reaction of
[PtMe2(bu2bpy)] with 1,2- dibromoethane affords the mononuclear complex of trans[PtMe2Br{(CH2)2Br}(bu2bpy)]. The effect of the imine and halogen will be discussed. The structure
of the resulting complexes was easily deduced from 1H and 13C NMR data and elemental analysis.
Keywords: Platinum, Oxidative Addition, Complex, Spectroscopy
P-194
Synthesis, characterization and catalytic studies of new unsymmetrical tetradentate
Schiff base complexes of oxovanadium(IV)
a
Sa'id Etminania, Mahdi Behzada,*
Faculty of science, department of chemistry, Semnan University, Semnan, Iran
The principal objective of this study is the determination of the catalytic performance of a series of
new oxovanadium (IV) complexes with {N-(R-Salicylidene)-N'-(salicylidene)-4-nitro-1,2phenylenediamine} (VOL1-3), in which R= 3-Methoxy (L1), 5-bromo (L2), 3-Nitro-5-Bromo (L3). The
tetradentate ligands (L1-3) were synthesized by the reaction between {N-(R-salicylidene)-4-nitro-1,2phenylendiamine} and salicylaldehyde both as solvent and reagent. These ligands were reacted
with vanadium oxide acetylacetonate to produce the target complexes [VOL1-3]. The products were
characterized by 1HNMR, IR and UV-Vis spectroscopies, cyclic voltammetry and elemental analyses
and melting points. The catalytic studies of the [VOL1-3] complexes in the epoxidation of
cyclohexene and cyclooctene were carried out and the progress of the catalytic reactions was
followed by gas chromatographic analysis (GC). The new catalysts show high catalytic activity and
excellent selectivity of the epoxidation.
Keywords: Oxovanadium; Schiff base; Tetradentate; Catalysis; Epoxidation
130
IICC12
P-195
Solvothermal Synthesis and Characterization Of BaCO3 Nanostructures
Sh. Ezatia, A. Hosseinianb, A. R. Mahjouba,*
Department of Engineering Science, University Colleges of Engineering, University of Tehran,
Tehran, Iran
a
b
Barium carbonate is an important material in industry for producing barium salts, pigment, optical
glass, ceramic,electric condensers, as well as its close relationship with aragonite, biomineral and its
use as a precursor for magnetic ferrites and/or ferroelectric materials. As a consequence,
controllable synthesis of BaCO3 with uniform size and morphology has attracted considerable
attention due to their novel properties and potential applications in a wide range of fields. Owing to
the important role of BaCO3, considerable works on synthesis and properties characterization of this
type of materials have been performed. The existing synthesis methods to nanostructures of
inorganic materials often demand the assistance of extra templates, catalysts, surfactants, etc.,
which undoubtedly cause a higher cost and a more complex purification procedure, or even worse,
a higher level of pollution to both the product and the environment. In this work, we report a novel
solvothermal synthesis of nanostructures of BaCO3 from an easily obtained inorganic single-source
precursor BaO2 without using any extra template, catalyst and surfactant. BaCO3 nanostructures
were synthesized by the reaction of BaO2 in ethanol by solvothermal method. The resultant
products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy
(SEM), and the Infrared spectroscopy (IR).
Keywords: Solvothermal, BaCO3, nanostructures, BaO2. SEM, XRD
P-196
Preparation and characterization of some metal alkoxide complexes
M. Faghani, M. Mirzaee,*, M. Bakherad and M. Khosravi
Department of Chemistry, Shahrood University of Technology, Shahrood, semnan, Iran
Metal alkoxide have been extensively investigated due to the potential application of them as
precursors for the oxide base ceramic materials, catalyst support, thin films and fibers via sol-gel
processing. However majority of metal alkoxide are very unstable toward hydrolysis and stabilizing
them with chelating functionalities are subject of interest and desire in sol-gel processing of
materials. For this purpose we have been prepared some metal alkoxide complexes with general
formula: M(OR)n(L)m in which M=Al, Ti or Nb and R=iPr, Et, sBu, tBu and L= Phendioxime,
benzoinoxime, pyridine-2-carbaldehydoxime, 4-tBu-benzyl alcohol and … . The structure of products
have been proposed according to the spectroscopic analysis (IR, NMR, Uv-Vis).
Keywords: Metal Alkoxide, phendioxime, benzoin oxime, pyridine carbaldehyde oxime, 4-tBubenzyl alcohol, Structure.
IICC12
131
P-197
Photoactive polymeric fibers based on zinc oxide nanoparticles: synthesis and
characterization
Hadi Fallah Moafi, Abdollah Fallah Shojaie*, and Mohammad Ali Zanjanchi
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran
Self-cleaning polymeric fibers have been successfully prepared by depositing ZnO nanoparticle onto
wool and polyacrylonitrile (PAN) fibers with good compatibility and significant photocatalytic selfcleaning activity using the sol–gel process at ambient temperature. Scanning electron microscopy
(SEM), Energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), diffuse
reflectance spectroscopy (DRS), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) surface
area analysis have been adopted as the characterization techniques. TEM studies revealed presence
of zinc oxide nanooparticles with 10-15 nm in size and BET measurement showed surface area 48
m2/g for the coated fibers. Photocatalytic activity of self-cleaning materials were tested by
measuring the photo-assisted degradation of methylene blue (MB) and eosin yellowish (EY) under
ultraviolet-visible illumination. The photoactivity results indicate that both of the ZnO-coated PAN
and ZnO-coated wool fibers show photocatalytic activity toward dyes degradation. This facile and
cheap preparation technique can be also applied to new polymeric fabrics to produce self-cleaning
materials for industrial application.
Keywords: Zinc oxide nanoparticle; Photocatalytic activity; Polyacrylonitrile; Sol-gel; Self-cleaning
materials; Wool
P-198
Photoactivity and flame-retardancy properties of cellulosic fibers modified by nanosized zinc oxide coating
Hadi Fallah Moafi, Abdollah Fallah Shojaie*, and Mohammad Ali Zanjanchi
Department of Chemistry, Faculty of Science, University of Guilan, P.O.Box 1914, Rasht, Iran
E-mail: [email protected],
In this paper, we have investigated effect of zinc oxide as a photo-catalyst and durable flameretardant on cellulosic fibers. Zinc oxide nanocrystals were successfully synthesized and deposited
onto cellulosic fibers properties using sol–gel process at low temperature. The samples were
characterized by means of several techniques such as scanning electron microscopy, transmission
electron microscopy, diffuse reflectance spectroscopy, X-ray diffraction and thermogravimetric
analysis. The photocatalytic activity was tested by measuring the photo-degradation of methylene
blue and eosin yellowish under ultraviolet-visible illumination. Moreover, flame-retardancy was
tested through by means of vertical flame spread test, and the optimum add-on value to donate
flame-retardancy onto cellulosic fabric was obtained to be in the range of 15.24 to 23.20 g of the
ZnO per 100 g fabric. Thermogravimetric analysis of pure and flame-retarded sample was
accomplished and discussed. The results obtained are in agreement with Wall effect theory and
Coating theory. The originality of this work for introducing photoactive-flame-retarded fibers is
highly valuable for industrial implementation.
Keywords: Cellulosic fiber; Flame-retardancy; Photocatalysis; Self-cleaning; Zinc oxide coating
132
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P-199
Synthesis of metal complex supported on functionalized MCM-41 and study of catalytic
behavior of product
Abdollah Fallah Shojaie*, Seyed soran ashrafi and Hadi Fallah Moafi,
In present work, mesoporous silica (MCM-41) was prepared and after characterization by low angle
X-ray diffraction and IR spectroscopy grafted by various amount of trymethyl aluminum and diethyl
zinc. Calcinations of grafted materials resulted to formation of aluminum and zinc doped materials.
Concentration of aluminium and zinc in all samples was measured by ICP and then their catalytic
activities have measured in esterification of phtalic anhydride and isoamyl alcohol. Result of
esterification with mesoporous silicas that doped with Si to aluminium ratios of 20, 10, 5 shows that
the Si to aliuminium ratio of 20 is the best among them. The zinc doped mesoporous silicas also
used in esterification and analysis of products show that the zinc doped mesoporous silica with Si to
Zn ratio of 20 is best in comparison to 5 and 10 ratios. Esterification reactions was also carried out
with uncalcined mesoporous silicas which aluminum and zinc grafted on external surface and
esterification yields was compared to these of mesoporous silica that their external and internal
surface grafted with aluminum or zinc. Results show the rate of esterification for molecule such as
phtalic anhydride is lower than that of for small alcohol like adipic acid.
Keywords: MCM-41 , Catalytic behavior, Metal complex , Supported
P-200
Surface modification of nano-crystaline hydroxyapatite with semiconductor and study
of photocatalytic properties of products
Abdollah Fallah Shojaie*, Mohammad Javashi and Hadi Fallah Moafi,
Hydroxyapatite nano-materials were synthesized by precipitation method. The synthesized powders
were characterized in term of structure (FT-IR and XRD), particle size and morphology (SEM and
TEM). Hydroxyapatite crystalities were in hexagonal structure. XRD pattern confirmed the
crystalline structure of hydroxyapatite. Then, Hydroxyapatite/TiO2 nanocomposite was successfully
synthesized by sol-gel method. The composite was characterized by various method including FTIR, XRD, SEM and EDX. The XRD patterns indicated the anatase phase for TiO2. Finally, the
photocatalytic activity of hydroxyapatite/TiO2 nanocomposite was examined by decomposition of
paracetamol (acetaminophen) and diclofenac in their aqueous solutions under UV-Vis irradiation.
The influence of some parameters on the degradation of these pharmaceutical compounds, such as
initial drug concentrations, initial PH value, time and photocalyst loading was studied to determine
the optimal operating conditions for degradation in water. The results indicated that
hydroxyapatite/TiO2 assisted photocatalytic degradation is a highly effective way to remove
paracetamol and diclofenac from wastewater and drinking water.
Keywords:
Diclofenac
Hydroxyapatite,
Nanocomposite,
Photocatalytic
degradation,
Paracetamol
and
IICC12
133
P-201
Synthesis and characterization of Cu2+and Ni2+ complexes of two tridentate hydrazone
Schiff bases
E. Farajzadeha , B. Shaabanib,* ,N.hajizadehc ,S.baghbanic ,E.nikjooc ,R.shafiee zadehc ,
M.khan soltanic ,F.khosravic
a
young researchers club, Islamic Azad University Ardabil Branch, Ardabil, Iran
b
c
Department of chemistry, Islamic Azad University Ardabil Branch, Ardabil, Iran
Chelating ligands play a central role in the developmentof the coordination chemistry related to
enzymatic reaction, magnetism, molecular architectures and transition metal catalysts for
oligomerization and polymerization of olefins in both academic and industrial sectors. Amongst
them, the enduring popularity of tridentate Schiff bases stems from the ease with which they can
be synthesized, their versatility and their wide ranging complexing ability.Schiff base hydrazone
ligands have attracted great and growing interest in chemistry and biology for many years due to
their facile synthesis and wide applications. Schiff base complexes have remained an important and
popular area of research due to their simple synthesis, versatility and diverse range of applications.
Here we report the synthesis and characterization of two tridentate Schiff-base ligand from the
reaction of 3-hydroxy-2-naphthohydrazied with 5-Iodosalicylaldehyde and 5-Nitrosalicylaldehyde,
Figure 1, and its complexes with Cu2+ and Ni2+ cations. The complexes were characterized with
IR, Uv/Vis and conductance measurements.Comparison of spectroscopic results for the ligand and
complexes and also visible absorption spectra for complexes suggest that ligand act as a tridentate
and coordinates via two oxygen and imine nitrogen atoms.
Keywords: Schiff-base, complexe, Transition metal cations
P-202
Synthesis and spectroscopic identification of some new complexes of IIB transition
metal ions
S. Farhadian and Morteza Montazerozohori*
Department of Chemistry, Yasouj University, Yasouj, Iran, E- mail:[email protected]
Metal complexes with asymmetric compartmental ligands have been the focus of extensive studies
because of their applications in several areas of chemical research. The field of Schiff bases
complexes is fast developing on account of the wide variety of structures possible for the ligands
depending upon the aldehyde and amines. Schiff bases play a central role as chelating agents for a
large number of metal ions, as they form stable five- or six-membered rings after complexation with
the metal ion. They can also be used as analytical, biochemical, and antimicrobial reagents. Schiff
base metal complexes have been a widely-studied subject because of their industrial, antifungal
and biological applications. In this work we wish to report the synthesis of some new four
coordinated complexes of IIB group transition metal ions with the ligand of N,N′-bis((E)-3phenylallylidene)phenylenediamine. The ligand and complexes were full characterized by physical
and spectral data including microanalysis, FT-IR, UV-Vis, 1H and 13C NMR and conductivity
measurements. The analytical data results the 1:1 ratio between the ligand and related salts. The
notable changes in the UV-Vis, IR and NMR spectra confirm the coordination of ligand.
Keywords: Complex, Bidentate, Schiff base, Phenylpropenal.
134
IICC12
P-203
Synthesis, Characterization and Crystal Structure Determination of Two Novel Proton
Transfer Supramolecular Systems
a
A. Farshadya, R. Alizadeha*, R. Hashemzadeha
(*e-mail: [email protected])
Two three-dimensional self-assembled proton-transfer compound, were synthesized from the
reaction of Pyrazin-2,3-Dicarboxylic acid with 2,6-pyridinediamine [(pyda.H)+(pyzdc.H)-.H2O] (1)
and 1,10-Phenanthroline [phen.H)-(pyzdc.H)+.2H2O] (2). The characterization was performed using
elemental analysis, IR, 1H NMR, 13CNMR spectroscopy and single crystal X-ray diffraction method.
Compound (1) crystallizes in the space group p21/c of the monoclinic system and contains four
molecules per unit cell. The unit cell dimensions are: a = 7.9057(8) Å, b = 6.6998(4) Å, c =
23.802(2) Å and β = 98.61(8)°. Compound (2) crystallizes in the space group C2/c of the
monoclinic system and contains eight molecules per unit cell. The unit cell dimensions are: a =
17.098(2) Å, b = 12.0339(1) Å, c = 16.387(2) Å and β = 96.544(1)°. The anionic and cationic
components self assembled three-dimensionally via ion-pairing, H-bonding and π-π stacking and,
therefore, parallel sheets are formed. In these compounds a large number of hydrogen bonds are
observed. These interactions play an important role in the formation and stabilization of
supramolecular systems in the crystal lattices.
Key words: Proton-Transfer Compound, Hydrogen Bond, π-π stacking, Pyrazin-2,3-Dicarboxylic
acid, Crystal Structure
P-204
Synthesis and characterization of two new bimetallic Mn-Cu complexes constructed by
chelate Cu cations and Mn dicyanamide polymeric chains
Javad Farzanfar and Ali Reza Rezvani*
Department of Chemistry, Universityof Sistan and Baluchestan, Zahedan, Iran
( e-mail: [email protected] )
It has been found that the network topology of anionic coordination polymers like M(dca)3 − and
M(dca)42− is dependent on the organic counter cation used or cation-templated, thus using cations
of metal complex to construct heterometallic assemblies having new structural and magnetic
properties is realized. In this study, two new bimetallic, Mn-Cu complexes,
[Cu(H2dipic)(H2O)3][Mn(dca)3].NO3 and [Cu(H2dipic)(H2O)][Mn(dca)4] (where H2dipic = dipicolinic
acid ) have been synthesized and characterized by elemental analysis, FT-IR, UV-Vis spectroscopic
and cyclic voltammetry methods. The IR spectrum of these complexes show strong absorptions in
the 2239-2142 Cm-1 region, corresponding to the νs+νas(C≡N), νas(C≡N), and νs(C≡N) modes of the
dca ligand. The shift toward higher frequencies of these peaks, when compared with those of the
free dca in its sodium salt (strong peaks at 2282, 2232 and 2129 Cm-1) is consistent with the
coordination of the ligand. The cyclic voltammograms at glassy carbon disc as a working electrode
for these complexes display three reduction processes. The strategy used in the current work can
be applied in constructing other heterometallic coordination polymers with various topologies and
magnetic properties.
Keywords: Mn-Cu complexes, Dicyanamide, Dipicolinic acid, Cyclic voltammetry
IICC12
135
P-205
Aromatic character studies on triafulvalenes, and its derivatives via nuclear
independent chemical shifts (NICS)
a
E. Vessally a* S. Fateh Basharzad b, H. Shabrendi b
Islamic Azad University, Miyaneh Branch, Miyaneh, Iran
b
Payame Noor University (PNU), Zanjan, Iran
triafulvalenes,is a completely conjugated unsaturated molecule. Many works have been done on
triafulvalenes. In this work, DFT calculations were carried out on molecular structure of
triafulvalenes and triafulvalenes-like containing heavy atoms, 1X and 2X (X=C, Si, Ge, Pb, N, P, As,
and Sb), using 6-311++G** basis set of the GAUSSIAN 98 program. The aromatic character of 1X
and 2X was investigated through magnetic and geometric criteria. From geometric view, molecules,
1Ge, 1pb , 1Si and 2As, 2Ge, 2Si , have completed electron current in the three-member ring(without
heteroatom). Nuclear independent chemical shifts NICS (0.5) calculations clarified an aromatic
character in both three rings of 1X and 2X, which was decreased from X=Ge to X=C. However, the
aromatic character in 2X ring were decreased from X=N to X=C. The details and related discussions
would be presented.
P-206
Photocatalytic reduction of Cr(VI) using Co-doped ZnO in aqueous solution
Sh. Fathi, A. Roshan, A. Fallah Shojaee*
Co-doped ZnO nanoparticles with different Co contents were prepared by co-precipitation method.
The materials characterized by XRD, SEM and TEM techniques. The effect of Co loading on the
photocatalytic activity of Co-doped ZnO in the degradation of Cr(VΙ) was studied and the results are
compared with the pure ZnO. The results showed that the rate of degradation of Cr(VΙ) over Codoped ZnO is much higher as compared to that of pure ZnO. The photocatalytic reaction were
carried out under solar radiation towards reduction of Cr(VI) by varying different parameters such
as irradiation time, pH of the solution, catalyst amount and substrate concentration.
Keywords: Photocatalytic reduction, ZnO nanoparticles, Cr(VI) elimination, Environmental pollution
136
IICC12
P-207
Synthesis, characterization and grafting of complexes with optical and radio
pharmaceutical properties on MCM-41 mesoporous silica
Y. Fazaeli a,b, M.M.Aminia*, A.R. Jalilian c , M.R. Aboudzadeh b and A.Rahimi nezhad b
Department of Chemistry Shahid Beheshti University G.C., Tehran 1983963113, Iran
b
Agricultural, Medical and Industrial Research School (AMIRS-NSTRI), Karaj, Iran 31485-498
Radiopharmaceutical Research and Development Lab (RRDL), Nuclear Science and Technology
Research Institute (NSTRI), Tehran, Iran, Postal code: 14155-1339
a
c
Interest in light-emitting diodes continues to thrive due to the high demand in medical diagnostic,
cell imaging and photonic device industries for such materials. Among organic light emitting
materials, metalo-(8-hydroxyquinoline) (HQnM) and its derivatives are unique electron transport
and emitting materials and have widely been used in optics and medicals such as tumor imaging. In
this study, we investigated the possibility of incorporating 8-hydroxyquinoline complexes of various
metals such as Aluminum, copper, zinc, gold and lanthanides series, on MCM-41 as fluorescent
materials, for use in tumor imaging and precursor for light emitting diodes. These materials were
bind on MCM-41 with or with out interface. The photoluminescence (PL) properties of grafted
complexes were investigated. The results revealed that the maximum wavelength is modulated by
the MCM-41 guest.
Keywords: Optical and Radio Pharmaceutical Properties, mesoporous silica
P-208
Pyridine-Functionalized MCM-41 as an Efficient and Recoverable Catalyst for the
Synthesis of Heterocyclic Systems
, Yousef fazaeli a,b, M.M.Amini b*, A.R. Jalilian c , M.Ghannadi -Maragheh c
,M.R.Aboudzadeh,b
a
Agricultural, Medical and Industrial Research School (AMIRS-NSTRI), Karaj, Iran 31485-498
b
Department of Chemistry Shahid Beheshti University G.C., Tehran 1983963113, Iran
Radiopharmaceutical Research and Development Lab (RRDL), Nuclear Science and Technology
Research Institute (NSTRI), Tehran, Iran, Postal code: 14155-1339
Shahzad feizi
c
a,b
The mesoporous molecular sieves such as MCM-41 which discovered by Mobil researchers in 1992,
have large and uniform pore sizes, ultrahigh surface areas, large pore volume and rich silanol
groups in the inner walls. The developments of mesoporous silicas such as MCM-41 have generated
interest due to their potential applications such as catalysts, catalyst supports, separation media,
and host materials for inclusion compounds. Furthermore, because of special texture and properties
of MCM-41, it has great potential as a matrix for immobilizing homogeneous catalysts. The aims of
the present investigation are to solve the problems of using homogeneous catalyst such as
separation and regeneration. As shown in figure 1, pyridine functionalized mcm-41 act like free
pyridine. The present method has the advantages that not only the catalyst can be recycled and
reused for several times without loss of performance, but also the substances can be mixed without
any modification.
Keywords: Pyridine-Functionalized MCM-41, Catalyst, Heterocyclic Systems
IICC12
137
P-209
Ligand substitution effect of Co(salen) on the oxidation catalysis of [60]fullerene
SH. R. Ferdosi, B.Ghanbari*
Department of Chemistry Sharif University of Technology, Tehran, Iran
[email protected]
The design of a system to probe variation in the reactivity of a bound O2 is complicated process.
The problem is, how to selectively oxidize a substrate without destroying the reagents in free
radical reactions with oxygen. Co(II) complexes of Schiff bases are among the well-known
dioxygen-activating species. Herein, the effect of ligand variation in Co-SALEN-type complexes on
anti-oxidative properties of fullerene in the presence of O2 in cumene was investigated. A
comparison was made between efficiency of Co(salen) as a catalyst by changing substitution on the
ligands. Reaction was followed by monitoring gaseous oxygen uptake by the cobalt (II) complexes
in cumene. It was found that the electron-withdrawing substituents on the Schiff bases decrease
the activity of the bound O2. Furthermore, the radical sponging property of [60] fullerene makes it
an anti-oxidant towards cumene oxidation. The feature was shown in Figure 1b in terms of O2
uptake by the complex in the presence of C60 which have been decreased in all of the cases except
for SalenαMe. Experimentally, it seems that C60 shows different effects in the presence of the
complexes by the following order: SalenBr2=SalenBrOMe>Saloph>Salen >SalenαMe
Keywords: Fullerene; CoSALEN; catalyst;Oxidation
P-210
Vanadyl and Molybdenyl acetylacetonate anchored onto imidazolinium choloride
alkylamine-functionalized polystyrene
a
Vida Tahmasebia, Gholamhossein Grivania,*, Zahrasadat Jaddia,
Damghan University, Damghan, P. O. Box 36715-364, School Of Chemistry, Iran
Heterogenization or immobilization of active metal complexes on polymeric supports has evolved as
a promising strategy for combining the advantages of homogeneous and heterogeneous catalysts
due to their easy isolation from the products by filtration and the possibility of recycling them by
continuous operation in a reactor. Transition metal complexes of Ti(IV), Mo(VI), Mn(III), Cr(VI) and
Fe(III) with polymer-supported Schiff bases have been shown to be active catalysts for oxidation
of alkene in presences of hydrogen peroxide, PhIO, tert-butyl hydroperoxide, NaOCl ,etc., as the
oxidants. In this research we report the immobilization of MoO22+ and VO2+ moieties on polystyrene
and catalytic activities of these catalysts in epoxidation of cyclooctene. Choloromethylated
polystyren was reacted with imidazole and by reaction of obtained resin with bromoethyl aminium
hydrobromide polymer-bound imidazolinum ethlyl amine was prepared. In subsequent reaction of
this imidazolinum functionalized polystyrene containing pendant amine group with MoO2(acac)2 and
VO(acac)2 in two separated reactions polymer-supported
catalysts were prepared that were
showed high activity epoxidation of cyclooctene.
Keywords: Polymer-support; Molybdenyl dication; Schiff base complex; Epoxidation.
138
IICC12
P-211
Ionic Liquids: Synthesis and Characterisation of Triphenylphosphonium
pentachlorohalophosphate (C6H5)3PH+[PCl5X]-, (X=F, Cl, I) , (TPPPCHP)
Gita Geimachy1, Shahriar Ghammamy
Kheyrollah Mehrani1 , Tahmineh Banibairami1 and Hossein
Tavakol3
1
2
3
Department of Chemistry, Faculty of Science, Zabol University, Zabol, Iran
[email protected] or [email protected]
,
*, 2
,
The field and phenomenon of room-temperature ionic liquids are now well past infancy, but much
work remains to be done to fulfill the true potential of these neoteric solvents. As the global leader
in the production of phosphine and phosphine derivatives. In this study, we report on the synthesis
and characterization of three new ILs compounds with triphenyl Phosphonium cations and different
anions such as [PCl5X] (X=F,Cl,I) by using straight forward precipitation reactions. During this study
we report the optimized geometries and infrared spectral measurements, 31P-NMR
spectroscopies,Thermal analysis TGA and DTA, CV, physical properties of viscosity and density the
room-temperature ionic liquids, assignments and electronic structure calculations for new ILs. The
structures of ILs have been optimized by the density functional theory (DFT) based method at
B3LYP/6-311G levels of theory, using the Gaussian 03 package of programs [6- 10].The comparison
between theory and experiment is made.
Keywords: room-temperature ionic liquids (RTIL), infrared spectral measurements, TGA , CV , 31P
-NMR , , physical properties of viscosity and density , electronic structure calculations for new ILs
P-212
Synthesis and Characterisation of New Family of Boron-Based Anion Compounds
Gita Geimachy1, Shahrzad Keysan 1, Shahriar Ghammamy *, 2, Roghayeh Pooseh 1and Tahmineh
Banibairami1
1
2
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Ghazvin, Ira
In several recent publications we have described our studies of the infrared spectra, in cryogenic
matrices, of the dimer of the Lewis acid boron trifluoride and of a variety of 1:1 Anion Compounds
of boron trifluoride with some common Lewis bases. In this study, we report on the synthesis and
characterization of tow new anionic compounds with Na+ cation and different anions such as [BF3X]
(X=F,I) by using straight forward precipitation reactions. During this study we report the optimized
geometries and infrared spectral measurements, Mass, UV/Visible and 11B-NMR spectroscopies,
Boron-Based Anion nano Compounds properties, assignments and electronic structure calculations
for compounds. The structures of compounds have been optimized by the density functional theory
(DFT)-based method at B3LYP/6-311G levels of theory, using the Gaussian 03 package of
programs. The comparison between theory and experiment is made.
Keywords: Anion Compounds , IR , Mass, UV/Visible , 11B-NMR , Synthesis, nano Compounds
IICC12
139
P-213
Synthesis, characterization of two new phosphates ionic liquids
Gita Geimachy1, Monir alihosseinzadhe1, Shahriar Ghammamy *, 2, Tahmineh Banibairami1 and
Hossein Tavakol3
1
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Iran,
Young researchers club (Ardabil branch.) Iran
2
Department of Chemistry, Faculty of Science, Imam Khomeini International University,
Ghazvin,Iran.
3
Department of Chemistry, Faculty of Science, Zabol University, Zabol, Iran
Room temperature ionic liquids (RTILs) have attracted remarkable scientific activities because they
have many astonishing properties, such as high catalytic activity, nonvolatility, thermal-stability, and
large liquid range, etc.. The field and phenomenon of room-temperature ionic liquids are now well
past infancy, but much work remains to be done to fulfill the true potential of these neoteric
solvents. As the global leader in the production of phosphine and phosphine derivatives. In this
study, we report on the synthesis and characterization of tow new anionic compounds with K+
cation and different anions such as [PCl3X] (X=SCN,CN) by using straight forward precipitation
reactions. During this study we report the optimized geometries and infrared spectral
measurements, 31P -NMR , Mass, UV/Visible spectroscopies, assignments and electronic structure
calculations for new ILs. The structures of ILs have been optimized by the density functional theory
(DFT) based method at B3LYP/6-311G levels of theory, using the Gaussian 03 package of programs
[5, 6].The comparison between theory and experiment is made.
Keywords: room-temperature ionic liquids (RTIL), infrared spectral measurements, 31P -NMR ,
Mass, UV/Visible
P-214
Nanoporous Metal-Organic Framework [Zn(tp)(H2O)]; Hydrothermal Syntheses and
Crystal Structure
a
S.Geranmayeha, A. Abbasia*, A. Badieia
The hydrothermal reaction of 1,4-benzendicarboxylic acid (H2tp) with Zn(NO3)2.6H2O together with
NaOH at 473 K lead to nanoporous metal-organic framework [Zn(tp)(H2O)], which has been
characterized by means of single crystal X-ray diffraction. The crystal structure analyses show that
the title compound consists of Zn(II) center with tp units in which zinc is coordinated by four
oxygen atoms from four different tp ions and one water oxygen atom in a distorted trigonal
bipyramidal geometry, to form a three-dimensional interconnected framework. There is also
relatively strong hydrogen bond exists between the water molecules and the neighboring chain and
Zn-O bonds connect one chain to two neighboring ones. The powder X-ray diffraction (PXRD)
patterns show the same results in different 453, 473 and 493 K temperature.
Keywords: nanoporous metal organic framework, crystal structure
140
IICC12
P-215
How the dimensions of nano-silver glass structure
A. Ghadya, M. Jahanshahi, bA. Kiani
Department of Chemical Engineering, Islamic Azad University, Ayatollah.. Amoli
b
MSc, cellular and molecular biologist, Islamic Azad University Ayatollah .. Amoli
[email protected]
a
One of the coolest silver pigment is beginning with a colored surface layer by the colloidal silver
particles are formed, is consistent. Gary form as a result of silver ion exchange process occurs in
which silver near Bayonne glass transition temperature of glass into the building during the reaction
of silver ions Contact nano comes with a glass surface. Considering the various mechanisms
provided for by the researchers have presented silver stain, using spectroscopy uv, ED, Raman and
Transmission electron microscopy (TEM) and using different clay soil to form a dough coloring glass
formation silver,we discuss in this article.
Keywords:colloidal silver particles, glass building, nano, spectroscopy
P-216
Formation of 3D supramolecular network by C-H…π and C-H…O interactions from novel
tetra nuclear complex of lead (II) with terephthalic acid and 8-hydroxyquinolin, [Pb4(8Quin)4(tp)2(DMF)2]
a
A. Ghaemi a,*, S. Rayati b, B. Jahanpanaha and H. R. Khavasic
Department of Chemistry, Islamic Azad University, Saveh Branch, Saveh, Iran
b
Department of Chemistry, K.N. Toosi University of Technology, Tehran, Iran
c
Department of Chemistry, Shahid Beheshti University, Tehran, Iran
Compounds with backbones constructed by metal ions as "nodes" and polytopic organic ligands as
"linkers" form a family of polymers, which are called "coordination polymers" or "metal–organic
frameworks" (MOFs). These materials have attracted a great deal of attention in the past decade
which is mainly due to their potential application in such fields as in gas storage, gas/vapor
separation, size-, shape-, and enantio-selective catalysis, luminescent and fluorescent materials,
and drug storage and delivery have been explored. A novel two-dimensional coordination polymer,
[Pb4(8-Quin)4(tp)2(DMF)2]n (tp= terephthalic dianion, 8-Quin- = 8-Hydroxyquinolate and DMF= N,
N-dimethylformamide) have been synthesized and characterized by elemental analysis, FT-IR and
single crystal X-ray diffraction. The single crystal X-ray analysis shows that the complex is a twodimensional (2D) polymer and the dimensionality is further increased to 3D as a result of weak CH…π and C-H…O interactions. The coordination number in PbII ions in this complex is six, with
“stereo-chemically active” electron lone pairs, and the coordination sphere is hemidirected.
Keywords: Coordination
Supramolecular network.
polymer,
Terephthalate
anion,
8-Hydroxyquinolate,
Lead
(II),
IICC12
141
P-217
Synthesis and crystal structure of a novel two-dimensional coordination polymer of the
PbII complex based on the polypyridyl ligand 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz),
[{PbCl2}2(µ-tppz)]n
a
c
A. Ghaemi a,*, S. Rayati b, B. Jahanpanaha and H. R. Khavasic
Department of Chemistry, Islamic Azad University, Saveh Branch, Saveh, Iran
b
Department of Chemistry, K.N. Toosi University of Technology, Tehran, Iran
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran, Iran
The synthesis and investigation of new coordination polymers have been of great interest in the
fields of crystal engineering and coordination chemistry because of their potential applications and
intriguing variety of architectures and topologies. Over the last 10 years, numerous spectacular
coordination polymers have been reported, such as 1D-chains and ladders, 2D grids, and 3D
microporous networks. The different kinds of metal ions, the geometry of the organic ligands, the
solvent and the temperature are all important factors to synthesize desired metal–organic
frameworks (MOFs). The selection of bridging ligand is one of the key steps for synthesis. A novel
coordination polymer, [{PbCl2}2(µ-tppz)]n (tppz= 2,3,5,6-tetrakis(2-pyridyl)pyrazine) have been
synthesized and characterized by elemental analysis, FT-IR and single crystal X-ray diffraction. The
single crystal X-ray analysis shows that the complex is a two-dimensional (2D) polymer as a result
of chloride and tppz bridging ligands. The coordination number in PbII ion in this complex is seven,
and the coordination sphere is holodirected.
Keywords: Coordination polymer, 2,3,5,6-tetrakis(2-pyridyl)pyrazine, Lead (II), Polypyridyl ligand.
P-218
Synthesis Of ternary ONO Schiff bases of cadmium (ΙΙ) complexes and characterized
with electronic spectra and IR.
1*
Moloud ghafoori and 2Nasrin shojae
Department of chemistry, gachsaran university, Iran,
[email protected]
New ONO-chelated Cadmium (ΙΙ) complexes have been prepared and characterized. A new ternary
Schiff bases were synthesized with reflux derivation of 2-Aminophenols and salicylaldehyds (ratio
1:1) at room temperature. With thin linear chromatography (TLC) known that mechanism were
completed after 50 min. After that Schiff bases were soluted in ethanol then injected to solution of
cadmium. These reactions were completed at 100о c after 5 hours. These products were
characterized with UV, IR. The IR spectra of the complexes showed ν(C=N) of 1600 cm-1 [the IR
spectra of complexes shift to up field because we have strong intraction between metal and amino
site]. The electronic spectra of the complexes showed (Л Л*) of imine at 450 -500 nm. The
complexes have a distorted square planner geometry in which the ligand are coordinated to the cd
(ΙΙ) ion as uninegatively charged tridentate chelates via the amin nitrogen atoms. Geometry is
attributed to the restricted bite angles of the schiff base ligands. In conclusion, novel ternary cd (ΙΙ)
complexes were synthesized and characterized. All complexes are stable in air and have high
melting point (>250c). They are freely soluble DMSO but not soluble in water, ethanol, and DMF.
Keywords: Aminophenoles, Salicyladehydes, Schiff- base complexes, Ternary cadmium (ΙΙ)
complexes.
142
IICC12
P-219
RuCl3-catalyzed highly C3-selective Friedel–Crafts alkylation of indoles with alcohols
S.ghanbari niyaki ,K. Tabatabaeian *, N.O.Mahmoodi
Ruthenium compounds constitute a versatile class of catalysts for important synthetic
transformations in organic Chemistry. First, its ability to access 11 different oxidation states,
ranging from –II (d10) up to +VIII (d0) is (besides osmium) a unique feature within the periodic
table. besides ruthenium complexes demonstrate a variety of useful characteristics, which include
Lewis acid acidity, high electron transfer ability, much less expensive compared to other platinum
metals: Pd , Pt , Rh. We found that ruthenium (III) chloride hydrate smoothly catalyzes the reaction
of indoles and alcohols leading to C–C bonds in one pot, affording the desired adducts in high
yields. On the other hand, indole derivatives occur in many pharmacologically and biologically active
compounds. In particular, 3-alkylindole derivatives have significant medical importance. we
investigated the Friedel – Crafts allylic alkylation between indole and alcohol in order to develop
the reaction conditions.We found that in the presence of RuCl3 (10 mol %) at room temperature in
different solvents , the reaction proceeded efficiently to afford the product in good yield.
Keywords: Ruthenium , indole , Friedel–Crafts
P-220
Efficient Conversion of Acetophenones to 1,3,5-Triarylbenzenes
R. Ghanbaripour, I. Mohammadpoor-Baltork, M. Moghadam, A. R. Khosropour , V. Mirkhani, S.
Tangestaninejad
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan, 81746-73441, I. R. Iran
1,3,5-Triarylbenzenes are important compounds in conducting polymers, electrode and
electroluminescent devices and resist material. These compounds are obtained by coupling of 1,3,5tribromobenzene and aryl boronic acid in the presence of Pd(PPh3)4. These compounds are also
prepared by triple self-condensation of aryl methyl ketones and acetophenone dialkylketals in the
presence of catalysts such as TiCl4, SiCl4, SnCl4 and ion exchange resins.These methods often
involve the use of large amounts of catalysts which are expensive, air sensitive and or toxic. Also
some of these methods suffer from disadvantages such as low yields, long reaction times and
tedious work-up. Recently, heteropoly acids have attracted attention of chemists because they are
relatively non-toxic, reusable and readily available. These compounds have been used as effective
catalysts in several organic transformations. In this work, an efficient method for the preparation of
1,3,5-triaryl benzenes from acetophenones and aryl methyl ketones in the presence of
tungstophosphoric acid is reported. The experimental results show that acetophenones with
electron-donating and electron-withdrawing substituents are converted to their corresponding
triarylbenzenes in high yields.
Keywords: 1,3,5-Ttriarylbenzenes, Heteropoly acids, Triple self-condensation
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143
P-221
Preparation and single structure determination of Pb(II) coordination polymer
containing mixed ligands
Ali Reza Ghanbarpour, Mostafa M. Amini*, Gholamhossein Mohammadnezhad
Department of Chemistry,Shahid Beheshti University, G.C., Tehran, Iran
Supramolecular metal complexes formed by some mixing ambidentate ligands are frontier field in
crystal engineering research because of their potential applications in catalyses, molecular
recognition, molecular electronics and photonic materials. For this purpose, a metal template with
appropriate organic blocker and a bridging agent are necessary. Azide and ambidentate ONO
ligands are interesting bridging agents which form a wide variety of networks with various transition
and main groups metals. The lead(II) complexes with N and O-donor bridging agent have been
studied in some details. The novel 1D polymeric Pb(ІІ) complex, [Pb2(Phen)2(N3)3(NO2)]n, containing
Pb2(µ-N3)3(µ-NO2) moiety, has been prepared and characterized by single-crystal X-ray diffraction.
This 1D coordination polymer has a novel Pb2(µ-N3)3(µ-NO2) bridged moieties. There is π-π
stacking between phenantheroline motives and Pb…N interactions in title compound which created
3D and 2D frameworks. The title complex was prepared by the convection tube and melting point
of this compound was 497 K.
Keywords: Supramolecular , lead(II) complex, ambidentate ligand , crystal engineering
P-222
Synthesis of Some Diorganotin(IV) Derivatives of NN- Chelating or O- Donor Ligands
B. Z. Momenia,*, R. Kiab and S. Ghanbarzadeha
Department of Chemistry, K.N. Toosi University of Technology,, Tehran, Iran
e- mail: [email protected]
b
Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
a
The diorganotin(IV) halides have a tendency to form 1:1 or 1:2 adducts with O- and N- donor
ligands. Accordingly, the interaction between tin(IV) and pyridyl ligand is of particular interest. We
have prepared eight new penta and hexa- coordinated diorganotin(IV) complexes derivatives of the
ligands
4,5bis(diphenylphosphino)-9,9-dimethyl-xanthen
(xantphos),
2diphenylphosphinoaminopyridine (dppap), 1,10- phenanthroline-5,6-dione (phendione) and
dipyrido-2,3-phenazine (dppz). Among them, xantphos and dppap act as a monodentate ligand in
solution to yield penta-coordinated complexes of [SnR2Cl2(xantphos)] and [SnR2Cl2(dppap)] (R =
Me, nBu). On the other hand, phendione and dppz act as a bidentate ligand toward the diorganotin
compounds and resulted in the formation of hexa-coordinated complexes of [SnR2Cl2(phendione)]
and [SnR2Cl2(dppz)] (R = Me, nBu). The resulting complexes have been characterized by
multinuclear NMR spectroscopy and elemental analysis.
Keywords: Organotin, Donor, Spectroscopy, Structure
144
IICC12
P-223
Fe3O4 nano particles: a powerful and magnetically reusable catalyst for the Biginelli
reaction
Abdol Mohamad Ghasemi, Bahador Karami* and Saeed Khodabakhshi
Islamic azad university of gachsaran, gachsaran, Iran
In recent years, Fe3O4 nanoparticles have attracted much attention. The direct use of Fe3O4
nanoparticles without modification as magnetically recoverable catalysts for organic reactions is
very rare. Beside this, the use of the solid state in chemical transformation conveys enormous
advantages in terms of separation and purification of materials. The technique of magnetic
separation, taking advantage of magnetic nanoparticles, is typically more efficient than
centrifugation or filtration as it prevents loss of the catalyst. Magnetic separation of the magnetic
nanoparticles is very simple, economical and promising for industrial applications. In this research, a
practical green chemistry procedure for synthesis of octahydroquinazolinone derivatives based on
Biginelli reaction between 1,3-cyclohexanedione, urea and appropriate aromatic aldehydes using
Fe3O4 nano particles as robust catalyst under solvent-free conditions was reported. Eco-friendly
nature of the catalyst, simple work-up procedure and the high yields of products, short reaction
times and avoid from using toxic organic solvents as media make this method a valid contribution to
the existing methodologies.
Keywords: Fe3O4 nano particles, Biginelli reaction, catalyst, octahydroquinazolinone.
P-224
ZnO Nanotubes as a Efficient catalyst for synthesis Bis(indolyl) Methanes derivatives in
room temprature
Ebrahim Niknam1, Mohsen Keshavarzi2,*,Abdolmohammad ghasemi2, Leila taghavi Moghadam3
1
Islamic Azad University of Kazron branch, Kazron, Iran
2
3
Bis(indolyl)methanes are most active cruciferous substances for promoting beneficial estrogen
metabolism and inducing apoptosis in human cancer cells. In recent years, synthesis of this class of
molecules under mild conditions have been reported,with promoters such as Montmorillonite clay K10 trichloro-1,3,5-triazine, 8 AlPW, sodium dodecyl sulfate(SDS), ZrCl4, In(OTf)3/ionic liquid,
CuBr2,MW/Lewis acids (FeCl3, BiCl3, InCl3, ZnCl2, CoCl2),NaHSO4 and Amberlyst, silica sulfuric
acid (SSA),metal hydrogen sulfates, NaHSO4/ionic liquid, CAN,NBS, and Ph3CCl. However, most of
the existing methods involve toxic metal ions and solvents, have high costs,use corrosive reagents
and have cumbersome work-up procedures. ZnO Nanotubes is found to be an efficient catalyst for
the condencation reaction of indoles with aromatic aldehydes toafford the corresponding bis
(indolyl) methanes in high yields in acetonitril solvent.The remarkable features of this new
procedure are high conversions, shorter reaction times,cleaner eaction profiles and simple
experimental and work-up procedures.
Keywords: Bis(indolyl)methanes; Carbonyl compounds; ZnO Nanotubes, aromatic aldehydes
IICC12
145
P-225
Synthesis, spectral characterization and structural analysis of new Mercury(I)
complexes
Hamideh Ghasemia, Saeed Dehghanpour*b and Ali mahmoudi
b
a
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
Four mercury(I) complexes, [L2HgHgL2](NO3)2 (L2 = (4-fluorophenyl)pyridin-2-ylmethylene-amine,
1; (4-chlorophenyl)pyridin-2-ylmethyleneamine, 2; (4-bromophenyl)pyridin-2-ylmethyleneamine, 3
and (4-iodophenyl)pyridin-2-ylmethyleneamine, 4) have been synthesized and characterized by CHN
analysis, IR and UV–Vis spectroscopy. Mercury (I) complexes with nitrogen ligands generally appear
to be unstable, although there are few exceptions (for example, the above noted complexes). This
apparent instability has been attributed to the tendency of such ligands to induce dismutation of the
mercury(I) ion due to the relatively greater stability of the corresponding mercury(II) complexes..
These complexes contain the Hg22+ moiety with mercury-mercury bonded core, which one diimine
ligand is coordinated to each mercury atom. Hg atoms have an additional axial interaction with the
oxygen atom of NO3- anion in both complexes. The complex 1 shows a step in Hg-Hg bond due to
the parallel configuration of the planar ligands. Supramolecular structures were built in both
complexe via π–π stacking of the diimine ligands. The average Hg–N bond distance (2.372 Å) is
similar to that found in structurally related complexes The diimine ligands in 1 are coordinated in a
slightly asymmetric bidentate manner: The difference between the bond lengths of Hg1–N1 and
Hg1–N2 is 0.11 Å. The Hg1–O1 distance is 2.490(9) Å, compared with the sum of the van der
Waals radii of 3.02–3.25 Å.
P-226
Novel Synthesis Of Doped Nano particle TiO2 With Anatase Framework For Stain
Resistance Cotton Fabric Application
S. Ghasemya, M.yousefib,*, kh. Farizadeh and R.Fazaeli ,B. kochaki
Department of Chemistry, Islamic Azad University Shahre-rey Branch, Tehran, Iran
c
Department of Engineering Chemistry loom, Islamic Azad University Shahre-rey Branch, Tehran,
Iran
d
Department of Chemistry, Islamic Azad University South-Tehran Branch, Tehran, Iran
e
Department of Engineering Chemistry loom, Islamic Azad University Shahre-rey Branch, Tehran,
Iran
Ce3+and Nd3+-doped nano structured TiO2 –and masked TiO2 with chitosan were prepared by solgel method. TiO2 were synthesis by the sol–gel method using tetra n-butyl ortho thitanat (TBT) as a
precursor. The prepared Ce3+doped TiO2/Nd3+nano particle characterization by X-ray
Diffraction(XRD), Scanning electron microscope (SEM), Analytical Element (EDS), Transmission
Electron Microscope (TEM). It can be observed that the major phase of the spectrum of nano
particle TiO2 was anatase and The morphology of the TiO2/ Nd3+ /Ce3+ microsphere was
investigated using SEM. Spectra IR indicates Ti-O bound is formed in the chitosan-TiO2 nano
composite through spectra IR and TiO2 is anatase in the nano composite toward XRD.
Photocatalytic properties of synthesized nano particles showed that decomposed azo dyes. One of
the most important application of nano particle TiO2 in textile industry product of stain resistance
cotton fabric, then in this research we studied about this effect of nano particle TiO2 on cotton
fabric .The results show that cotton fabric treatment with nano particle TiO2 has this properties.
a,b
Keywords: Sol-gel method , TiO2 Nano particle,Ce3+-doped
146
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P-227
Chromium (III) chloride hexahydrate as a powerful catalyst for the Pechmann reaction
Vahideh Ghashghaee, Bahador Karami*, Saeed Khodabakhshi and Farideh Abdali
Islamic azad university of gachsaran branch, gachsaran, Iran
Chromium salts have received a significant amount of attention in the recent literature as a
powerful catalyst for transition metal-catalyzed reactions. A type of Lewis acids such as CrCl3.6H2O
as transition metals were found to catalyze the reaction efficiently to furnish the heterocyclic
compounds such as substituted coumarins under solvent-free and thermal conditions. Coumarins as
containing oxygen compounds are very important for synthesis. Because of their biological
properties such as antibiotic, anti cancer, anti HIV, antifungal and also application in the perfumes,
dyes, optical brightness, additive in foods and insecticides, these compounds were broadly used in
the fields of industry and medicine. The Pechmann Condensation allows the synthesis of coumarins
by reaction of phenols with β-keto esters. In this research, an efficient method for simple
preparation of benzo-2-pyron derivatives via the Pechmann condensation between phenol
derivatives and
ketoesters using catalytic amounts of nickel sulfate heptahydrate (NiSO4.7H2O)
under solvent-free conditions was reported. The practical and simple method led to excellent yields
of the products under solvent-free conditions and within short time reaction. The advantages of this
method are simple, cheap and eco-friendly procedure, short reaction time and easily work-up of
pure product in high yields.
Keywords: Chromium (III) chloride hexahydrate, transition metals, catalyst, Pechmann reaction.
P-228
A Computational Study on some Lewis Acid–Base Adducts
H. Ghatezadeha, A. Akbaria,*, Y. Ebrahimipoura, M. Ahmadia, B. Golzadeha,b
a
Department of Chemistry, Payame Noor University (PNU), Mashad, Iran
b
Department of Chemistry, Payame Noor University (PNU) , Amol, Iran
The Lewis definition implies the presence of high electron density centers in Lewis bases, and low
electron density centers in Lewis acids.
A(g) + :B(g)
A:B(g)
And also:
∆E = EA:B – EA – E:B
In this study, a large group of compounds of the type MX3NX3 (M=B, Al, Ga, In, Tl; X=H, F, Cl, Br,
I, CH3, C2H5) have been studied theoretically and the HF ab initio and DFT methods have been
employed for the calculations. MX3 is used as the Lewis acid and NX3 as the Lewis base. Several
trends such as the energy level of HOMO and LUMO, partial charges on atoms and the effects of
donating and withdrawing groups have also been investigated which were not previously reported.
Figure 1 shows graphical presentation of frontier orbitals of the BH3NH3 adduct which shows the
electron density centered on B and N atoms in the HOMO and LUMO of adduct compound
respectively.
Keywords: Lewis Acid-Base Adduct, HF, DFT, HOMO-LUMO.
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P-229
Synthesis and Study of oxovanadium(IV)-tridentate Schiff base complex encapsulated
in zeolite-Y as catalyst for sulfide oxidation with UHP
Saeedeh Ghazali Esfahani, Mojtaba Bagherzadeh*
Chemistry Department, Sharif University of Technology, Tehran PO Box 11365-9516, Iran
*
E-mail address: [email protected] (M. Bagherzadeh)
The immobilization of transition metal complexes on solid support provide certain properties for
catalysts such as selectivity, thermal stability and recycle ability. Recently, zeolite encapsulated
metal complexes (ZEMC) are interested as heterogeneous catalysts for different processes. A
variety of oxovanadium(IV) complexes have been shown to catalyze the oxidation of sulfides by
using peroxides as oxygen atom donors. A oxovanadium(IV) complex of Schiff base derived from
salycylaldehyde and o-aminophenol ((2-(salicylideneamino)phenolate) is encapsulated in the nanocavities of zeolite-Y by flexible ligand method. The zeolite encapsulated complex shows high activity
and selectivity for oxidation of sulfides using urea hydrogen peroxide (UHP) as oxidant. The
conversion of methyl phenyl sulfide oxidation is 90% after 3 h with 83% selectivity to sulfoxide.
Keyword: Oxovanadium(IV) Schiff base, Zeolite, encapsulation, Sulfide oxidation, urea hydrogen
peroxide (UHP).
P-230
Catalytic Oxidation of Sulfides to Sulfoxide by Some cis-dioxomolybdenum(VI)
Tridentate Schiff base Ligands
Saeedeh Ghazali Esfahani, Mojtaba Bagherzadeh*
Chemistry Department, Sharif University of Technology, Tehran PO Box 11365-9516, Iran
*
E-mail address: [email protected] (M. Bagherzadeh)
The activity of molybdenum compounds has been extensively investigated as catalyst for different
processes, and this is supplemented by synthesis, characterization and reactivity studies of
numerous molybdenum dioxo complexes with various ligands. Cis-dioxomolybdenium(VI) complexes
are considered to be active catalyst for oxidation of sulfides. Several cis-dioxomolybdenum(VI)
complexes, with tridentate Schiff base ligands, derived from salicylaldehyde and aminophenols or oaminobenzenethiol (1-8) are examined as catalysts for oxidation of various sulfides with urea
hydrogen peroxide(UHP) as oxidant. Using these complexes as catalysts for the oxidation of methyl
phenyl sulfide as a typical substrate at room temprature gives sulfoxide with selectivity close to
85% and turnover frequency up to 290 h-1.
Keywords: cis-dioxomolybdenium complex, Schiff base, sulfide oxidation, urea hydrogen peroxide.
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P-231
Density functional theory studies on the conversion of verdoheme to ironbiliverdin
M. Gheidi, N. Safari*, M. Zahedi
Department of Chemistry, Shahid Beheshti University, Tehran, Iran
Heme degradation is an important reaction in the human body and as such has received significant
attention through extensive experimental and theoretical studies. The conversion of ferrous
verdoheme to ferric biliverdin in the presence of O2 was investigated using the B3LYP method. In
the first route oxygen and reducing electron were employed. In this path formation of ferrous
verdoheme-O2 complex was followed by the addition of one electron to the ferrous-oxycomplex to
produce ferric peroxide intermediate. The ferric peroxide intermediate experienced an
intramolecular nucleophilic attack to the most positive position at 5-oxo carbons on the ring to form
a closed ring biliverdin. Subsequently the ring opening process took place and the iron (III)
biliverdin complex was formed. In the second path a ferrous-O2 complex was formed and, without
going to a one electron reduction process, nucleophilic attack of Iron superoxide complex took
place followed by the formation of Iron (III) biliverdin. This path is thermodynamically and
kinetically less favorable than the first one. In addition, Iron hydro peroxy complex or direct attack
of O2 to macrocycle to form an isoporphyrin type intermediate have studied and results were
compared.
Keywords: Ferrous Verdoheme, Ferric Biliverdin, Density functional theory, Heme degradation
P-232
Preparation and Characterization of Ni-Al-No3 Layered Double Hydroxide
K.Nejatia , O. gheibia,* , R . zabihia , KH . yousefib
Department of Chemistry , Payame Noor University , Tabriz , Iran
Department of Chemistry , University of basic science , Damghan , Iran
a
b
Nano-technology is one of the most dynamic and fastest growing areas of research in the fields of
science ,engineering and medicine . Nanoscale materials exhibit unique properties compared to
their counterpart bulk materials . Layered Double Hydroxides (LDHs) , or so-called hydrotalcite-like
compounds , have attracted more and more attentions owing to potential application as anion
exchangers , adsorbent , medicine stabilizers , catalysts , solid-state nanoreactors and etc. Ni-AlNo3- LDHs were successfully synthesized from Ni( No3 )2 .6 H2o and Al( No3 )3 .9 H2o coprecipitation
method in constant PH 9.5 , at various temperatures and various Ni2+/Al3+ molar ratios in H2O and
mixture of H2O and alcohol as solvents . The samples were characterized by XRD . FT_IR and SEM .
All results showed that samples have synthesized pure with high crystallinity.
Keywords: Layered Double Hydroxides , coprecipitation , Ni2+ , Al3+ , XRD , SEM
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P-233
Experimental Kinetic Modeling of Oxidative Coupling of Methane in a Differential Fixed
Bed Reactor
Mahnaz Ghiasi1 , Samaneh Sadat Hoseini2 , Azim Malekzadeh1* , Abasali Khodadadi3 , Alireza
Talebizadeh3
a: School of Chemistry, Damghan University (DU), Damghan, I. R. Iran.
b: School of Chemical Engineering, Ferdowsi University of Mashhad (FUM), Mashhad, I. R. Iran.
c: Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering,
University of Tehran, Tehran, I. R. Iran. (E-mail: [email protected])
Kinetic of the oxidative coupling of methane (OCM) to ethylene and ethane over
(5%Na2SO4+4%Mn+3.13%W)/SiO2 catalyst was studied experimentally in a differential fixed bed
reactor at 800ºC, Gas Hourly Space Velocity (GHSV) 10250, 13400 hr-1 and different
methane/oxygen ratio. A lumped kinetic model containing main species of CH4, O2, COx (CO2, CO),
and C2 hydrocarbons (C2H4 and C2H6) was used. According to this mechanism methane is first
converted to ethane and COx in two parallel reactions and then ethane dehydrogenized to ethylene.
The model has been reported according to the GHSV and methane to oxygen ratio variation in
terms of partial pressure of oxygen. The model was validated against the experimental data and
was used to investigate several operating variables under the conversion and selectivity terms. The
main findings of this study are: The results of model agreed well with the experimental data at high
oxygen partial pressures (higher than 0.09 atm). By increasing the GHSV, the methane conversion
increased, whereas, C2 selectivity decreased. By increasing the CH4/O2 ratio, the methane
conversion was decreased while C2 selectivity was increased.
Keywords: Oxidative Coupling of Methane (OCM), Kinetic model, Differential reactor, catalytic
reactions mechanism.
P-234
Oxidative Coupling of Methane over Cerium and/or Tungsten Promoted Na2SO4/SiO2
Catalysts
M. Ghiasia , A. Malekzadeha* , A. Khodadadib , A. Talebizadehb
a: School of Chemistry, Damghan University (DU), Damghan, I. R. Iran.
b: Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering,
University of Tehran, Tehran, I. R. Iran. (E-mail: [email protected])
Oxidative coupling of methane (OCM), an attractive path for direct conversion of natural gas to C2
hydrocarbons,
was
studied
over
5%Na2SO4/SiO2,
(5%Na2SO4+4%Ce)/SiO2
and
(5%Na2SO4+4%Ce+3.13%W)/SiO2 catalysts in a fixed bed quartz micro-reactor under ambient
pressure at 775-825ºC using different oxidants. The catalysts were prepared by the incipient
wetness impregnation method and calcination at 800oC. Samples were characterized by XRD, ICP,
FTIR, Raman Spectroscopy and Flame Photometry. Electrical conductivity of the catalysts was
measured under the OCM and oxidant atmosphere. A direct relation was observed between catalytic
activity and electrical conductivity. It was observed that (5%Na2SO4+4%Ce+3.13%W)/SiO2 is the
most active / selective catalyst. The (5%Na2SO4+4%Ce)/SiO2 catalyst, however, shows a high C2
selectivity. To this end presence of the sodium, Cerium and tungsten species is critical for the
formation of an active / selective catalyst. A crystalline form, achieved during the calcination
catalyst at 800oC, is completed on reaction.
Keywords: Oxidative Coupling of Methane (OCM), Na2SO4, C2 hydrocarbons, Crystalline form,
Electrical conductivity
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P-235
Application of new nickel(II) thiosemicarbazone supported on nano porous silica as a
selective catalyst for oxidation of alcohols
A. Gholami a, M. Hakimi a,*, R. Takjoob, T. Tabarib
Department of Chemistry, Payame Noor University (PNU), Mashhad, Iran
Department of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad 917751436, Iran
a
b
Applications of metallic complexes as homogenous and heterogeneous catalyst have been
considered and meanwhile salen, salophen and porphyrin complexes more than other coordination
compounds as catalyst have been studied and investigated. For this purpose, thiosemicarbazone
complexes because different ability that can be created through variety synthesis methods is a
suitable convene. In this abstract we have demonstrated the utility of new Ni(II) thiosemicarbazone
supported on nano porous silica catalyst in the oxidation of primary and secondary alcohols to
carbonyl compounds with H2O2. This catalytic system has some advantageous: (I) mild reaction
conditions (room temperature); (II) nontoxicity of the catalyst; (III) the use of supported Nicomplex provides an easy way to recover and recycle the catalyst from the reaction media; (IV)
excellent selectivity; (V) low cost; (VI) short reaction times. The catalyst has appropriate selectivity
for primary alcohols from two probable acids and aldehydes products only acids were generated.
Also, for secondary alcohols only ketones was made. In the absence of catalyst, the reaction was
much less efficient for the conversion of alcohols to acids or ketones. The effect of different
solvents was studied in the oxidation of benzyl alcohol, CH3CN was better solvent.
Keywords: Selective Oxidation, Encapsulated nickel thiosemicarbazone complex, Hydrogen
peroxide, Alcohol
P-236
Substitution reaction on Zn-complexes
Gh.Gholami,H. A.Rasekh*,F.Karami Shirazi
Department of Chemistry,Islamic Azad University of Firooz Abad-Branch
Some Zn - complexes with sulfate and chloride as counter ion were synthesized and characterized .
First some complexes of zinc with ligands such as: oxalate , ethylene diamine , L-Lysine , L-Histidine
and L-Arginine were synthesized and by IR characterized . Then the substitution reactions of this
complexes with other ligands were studied . First synthesized complexes are K4[Zn(C2O4)3] ,
[Zn(en)3] (NO3)2 , [Zn(en)3] SO4, ,[Zn(L-Lys)2(H2O)2] Cl2, [Zn(L-Lys)2(H2O)2] SO4 ,[Zn(L-His)2(H2O)]
Cl2 , [Zn(L-His)2(H2O)2] SO4 , [Zn(L-Arg)2(H2O)2] Cl2 and [Zn(L-Arg)2(H2O)2] SO4 .Som of the
synthesized complexes are : [Zn(en)3] C2O4 , [Zn(L-Lys)2(H2O)2] C2O4 , [Zn(L-His)2(H2O)2] C2O4 ,
[Zn(L-Arg)2(H2O)2] C2O4 , [Zn(en)3] SO4 , [Zn(L-His)2(H2O)2] C2O4 , [Zn(L-Arg)2(H2O)2] SO4 , [Zn(LArg)2(H2O)2] SO4 , [Zn(L- Lys)2(H2O)2] SO4 , for example substitution reaction of k4[Zn(ox)3] with
ethylene diamine lead to formation of [Zn(en)3]C2O4 or substitution reaction of [Zn(L-His)2(H2O)2]
SO4 with L-Lysine lead to formation of [Zn(L-Lys)2(H2O)2] SO4 .The IR spectra clearly detect these
complexes.
Keywords: Substitution reaction,Zn-complexes, oxalate ,L-Lysine, L-Histidine ,L-Arginine.
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P-237
Syntheses, structure, electrochemical and spectroscopic studies Tricarbonylrhenium(I)
bromide complexes
b
Kamelia Gholamrezazadeha, Saeed Dehghanpour*b and Ali mahmoudia
a
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran,
Two rhenium(I) complexes, [Re(CO)3Br(Ln)] (n=1, 2), (L1 = N, N' Bis[1-(4chlorophenyl)ethylidene]ethane-1,2-diamine and L2 = N,N' Bis[1-(4-nitrophenyl)ethylidene]ethane1,2-diamine) have been synthesized and characterized by CHN analyses, 1H NMR, IR and UV–Vis
spectroscopy. The tricarbonyl rhenium (I) complexes are of growing interest as most of these
complexes combine remarkable features like ease of preparation, the unique photophysical and
photochemical properties of these species, and chemical stability. The IR spectra for complexes
exhibit three absorption bands in the carbonyl stretching region, as a sharp intense band at 2019
cm-1, and two closely spaced bands at 1914 and 1893 cm-1 for 1 and about 2024, 1917 and 1885
cm-1 for 2, typical of the fac-Re(I) diimine tricarbonyl complexes. The methyl protons of the
complexes show a singlet at ca. 2.2 ppm. The A4 system of the methylene for the ligands is
converted into an A2B2 system when the complexes are formed. The UV–Vis spectra of the
complexes are characterized by first metal to ligand charge transfer bands increasing in wavelength
when the L2 ligand is replaced by L1, in good agreement with the oxidation potential of the
complexes.The electrochemical behavior of the complexes was examined by means of cyclic
voltammetry in CH3CN.
P-238
A computational study on the prediction of the formation of “1 + 1” versus “2 + 2”
macrocyclic Schiff base complexes
Yasin Gholi ee, Fereshteh Yaghoobi, Mehdi Bayat, Sadegh Salehzadeh*,
The size and electronic nature of the cation used as the template agent in cyclocondensation
reactions has proved to be of importance in directing the synthetic pathway and resulting products
[1]. There are several reports for synthesis and characterization of “1 + 1” and “2 + 2” Schiff base
complexes in the presence of various metal ions. However, in best of our knowledge, the
computational prediction of latter “1 + 1” versus “2 + 2” cyclocondensation reactions has not been
reported.[2-3] Thus, so far, it has not shown that without experimental efforts one can
computationally predict the type of cyclocondensation reactions among all possible types. All
calculations were performed at DFT(B3LYP) level of theory. Three different basis sets, LanL2DZ,
SDD and CEP-121G were used in order to check the possible effect of the basis set on the
resulting data. The counterpoise (CP) procedure was also used to calculate the basis set
superposition error (BSSE). Several coordinating anions, such as Br-, Cl-, SCN- and NCS- were also
considered for both the Pb(II) and Mg(II) complexes studied here to study the possible effect of the
coordinated anion on the formation of “1 + 1” versus “2 + 2” macrocyclic complexes. The results of
calculations were consistent with the experimental observations and all showed that “1 + 1” and “2
+ 2” macrocyclic Schiff base complexes are preferred products for Mg(II) and Pb(II) metal ions,
respectively.
Keywords: Preferential energy, DFT calculations, Cyclocondensation reactions, Macrocyclic Schiff
bases
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P-239
Theoretical studies on the proton affinities of some different series of 3Dmacropolycyclic polyamines and designing strong superbases
Yasin Gholi ee,a Zeinab Azizib , Leila Ebrahimkhani,b, Sahar Yaghoobi,b Mahdi Rezaei Sameti,b
Mehdi Bayat,a Sadegh Salehzadeh*,a
a
b
Strong super bases and particularly the so-called molecular proton sponges (PS) are subject matter
of continuous interest. Recently, it was pointed out that proton sponges belonging to a class of
poly(ethyleneimines) might play a key role in a new gene therapy. The numerous experimental and
theoretical studies have been performed in the past in order to elucidate properties of these strong
bases. Deman molecule, 1,8-bis(dimethylamino) naphthalene, is known as “proton sponge” because
of its high thermodynamic basicity combined with a kinetic inactivity to deprotonation that
resembles the affinity of a sponge for water. Herein we want to report a density functional theory
(B3LYP) study to determine the gas-phase proton affinities as well as basicity of of some different
series of 3D-macropolycyclic polyamines. We compare the basicity of latter ligands with that of
DMAN. All calculations were performed at DFT (B3LYP) level of theory using 6-31G** basis set. The
result showed that the present 3D-macropolycyclic ligands all are among strong super bases as
their basicity is greater than DMAN.
Keywords: Proton affinities, 3D-macropolycyclic, Strong super bases.
P-240
A theoretical study on Carbon-13 Chemical Shifts of Carbonyl Groups in Some M(CO)5X
(M=Cr or Mo and X=CO, CN or CH3CN) Metal Complexes; Excellent Correlations
with Experimental Data.
Yasin Gholi ee,a Zahra Monjezi,b Maryam Hatamib , Mahdi Rezaei Sameti,b Fereshteh Yaghoobi,a
Mehdi Bayat,a Sadegh Salehzadeh*,a
a
b
There are several minor problems associate with the measurements on 13C in organometallic
compounds such as low abundance of 13C isotope in sample, the nuclear relaxation time is often
long etc. that the theoretical methods could be easily solved them. In this work the structure and
13
C chemical shifts for carbonyl groups of a number of M(CO)5X complexes were investigated at
DFT level. We also report a comparison with corresponding experimental data. All calculations were
performed at B3LYP level of theory using 6-31G* basis set for C, H, N and O and DGDZVP basis set
for metal ion. The calculations of NMR shielding tensors were done using two common procedures,
namely GIAO and CSGT. The obtained shielding tensors were referenced against tetramethylsilane
(TMS) to yield relative chemical shifts { (cal) = (TMS, calc)
iso (calc)}. The results showed that
there is excellent correlation between the calculated chemical shifts with available experimental
data. The calculated chemical shifts for chromium complexes are greater than those for
molybdenum complexes.
Keywords: Carbon-13 chemical shifts, M(CO)5X complexes, TMS, Density functional theory study,
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153
P-241
Prediction of microscopic protonation constants of polybasic ligands via computational
methods. Complete microequilibrium analysis of two linear tetraamine ligands.
Yasin Gholi ee, Mehdi Bayat, Sadegh Salehzadeh*
The acid-base properties of polybasic ligands are usually characterized in terms of macroscopic
protonation constants which are composites of the microscopic constants for the individual basic
sites. The protonation microconstants are defined as specific basicity parameters of a particular
basic site, in a defined protonation state for all other basic sites in the molecule. Due to the
instantaneous character of the protonation reactions, microspecies are in incessant interconversion.
The coexistence and short individual lifetime preclude them from direct analytical determination by
any of the existing, fast experimental techniques. Thus, determination of microscopic protonation
constants, in contrast to macroscopic protonation constants, is relatively difficult (and in some cases
even impossible). Herein a simple methodology is reported for calculation of microscopic
protonation constants of polybasic molecules in solution theoretically. Density functional theory
study (DFT) was used for complete microequilibrium analysis of two linear tetraamine molecules
with general formula NH2(CH2)mNH(CH2)nNH(CH2)mNH2 (where m=n=3, L333; and m=3, n=4, L343
). A general thermodynamic cycle is proposed to calculate protonation microconstants of polybasic
molecules using calculated micro-∆G values in aqueous solution. The results show that for
spermine, L343, both the corrected calculated micro- and macroconstants have good agreement
with the corresponding available experimental data.
Keywords: Linear ligands , microconstants, Macroconstants, Theoretical studies, DFT calculations.
P-242
Preparation and characterization of H3[PW12O40] nanoparticles produced by an reverse
microemulsion method
Melika Ghorbani, Majid Masteri-Farahani
Department of chemistry, Tarbiat Moallem University, Tehran, Iran
Polyoxometalates (POMs) constitute a significant class of inorganic compounds with potential
applications in catalysis, conductivity, molecular electronics, photoelectronic and electronic devices.
Among a wide variety of POMs those belonging to the so-called Keggin series are of the most
impotance for recent applications. In recent years, PMO nanostructural materials have attracted
increasing attention owning to their remarkable properties. Usually tungsten heteropolyacids are the
catalysts of choice because of their stronger acidity, higher thermal stability and lower oxidation
potential compared to other heteropolyacids. In this work we have reported a reverse
microemulsion method for the synthesis of the H3PW12O40 nanoparticles. The cationic reverse
microemulsion system includes surfactant cetyltrimethylammonium bromide (CTAB)/isooctane/1butanol/water. Addition of aqeuous Na2WO4 and Na2HPO4 and then acidification with HCl resulted in
the formation of H3PW12O40 spherical nanoparticles. Characterization of the resulted nanomaterial
was carried out with FT-IR, powder X-ray diffraction (XRD) and scanning electron microscopy
(SEM). The size of the resulted approximately uniform nanoparticles is about 100 nm.
Keywords: nanoparticle, microemulsion, heteropolytungstate, H3[PW12O40].
154
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P-243
Silica supported metalloporphyrins as catalysts for oxidation of cyclohexane with
molecular oxygen
a,b
Z.Ghoreishia,*, R.Rahimib
Department of Chemistry, Iran University of Science and Technology, Tehran, Iran
Metalloporphyrins have been extensively explored as bio-mimetic catalysts, following the action of
cytochrome P-450. Althogh, the synthesis of metalloporphyrins is challenging with low-yield, But
immobilization of them onto a solid support enabling the easier recovery and reuse of the catalysts,
this makes them cost-effective and can also prevent molecular aggregation or biomolecular selfreduction reactions, which leads to deactivation of catalytic metalloporphyrin species. Within
different supports, the Silica gel as an inorganic support has advantages such as: high stability,
good accessibility, and good surface attraction towards functional groups of organic molecules. In
this work, the catalytic activity of immobilized 5,10,15,20-meso tetrakis-(p-chlorophenyl)porphyrin
iron(III) [FeIII(TClPP)] on modified silica gel has been studied. The silica gel was modified with 3aminopropyltriethoxisilane groups (SF-3-APTS). The hybrid materials as catalyst for the oxidation of
cyclohexane with activated molecular oxygen by N-hydroxyphthalimide(NHPI) were investigated. In
this regard, the SEM, GC, FT-IR and UV-Vis spectra were used for characterization of the above
materials. The results indicate that these new heterogenized catalysis are more efficient than the
analogous non-supported metalloporphyrins for oxidation of cyclohexane.
Keywords: Silica-metalloporphyrin, Cyclohexane, Catalysts, Oxidation.
P-244
Synthesis, Spectroscopic Characterization and Antibacterial Activity of New
Organotin(ІV) Complexes with N(4)-phenyl thiosemicarbazone Derivatives
a
A. Golalzadeha, T. Sedaghata*, H. Motamedib
Department of Chemistry, Shahid Chamran Cniversity, Ahvaz, Iran
b
Department of Biology, Shahid Chamran University, Ahvaz, Iran
Thiosemicarbazones have received considerable attention because of their biological activities
including cytotoxic, antibacterial, antitumor and antileukemic properties. In view of potential
applications of organotin(IV) complexes in medicinal chemistry and biotechnology, and their
structural variety, it is worthwhile to synthesize organotin(IV) complexes with substituted
thiosemicarbazones and investigate their structures and biological properties. In this research work,
N(4)-substituted thiosemicarbazones, H2L1 and H2L2, have been prepared by reaction of N(4)phenyl thiosemicarbazide with 5-bromo-2-hydroxybenzaldehyde and 2-hydroxynaphthaldehyde,
respectively. The organotin(IV) complexes [SnPh2L1], [SnMe2L1], [SnPh2L²], [SnMe2L²], [SnBu2L²]
were synthesized from reaction of SnR2Cl2 (R=Ph, Me, Bu) with related thiosemicarbazones. New
complexes have been characterized by elemental analysis, FT-IR, 1HNMR and ¹¹9SnNMR
spectroscopy. The antibacterial activity of all ligands and complexes was tested in vitro against two
gram-positive and two gram-negative bacteria and the activities were compared with standard
drugs.
Keywords: Phenythiosemicarbazone, Organotin(IV), Antibacterial activity,
119
Sn NMR
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P-245
A new dinuclear Cd(II) macrocyclic schiff base complex of an total asymmetric ligand
a
R. Golbedaghi*a S. Salehzadehb, R. Azadbakhta and H. Veisia
Department of Chemistry, Payame Noor University, (PNU), Iran
b
([email protected])
A large variety of [1 + 1] and [2 + 2] macrocyclic ligands have been synthesized to ascertain
correctly the role of the different donor atoms, their relative position, the number and size of the
chelating rings formed, the flexibility and the shape of the coordinating moiety on the selective
binding of charged or neutral species and on the properties arising from these aggregations. In
present work we report the synthesis and characterization of a new binuclear macrocyclic Schiff
base complex of Cd(II). [2+2] cyclocondensation of a total asymmetric L23py = N-(2-pyridylmethyl)N-(3-aminopropyl)-1,3-diaminopropane amino ligand and 2,6-diformyl-4-methylphenol, dfp, in the
presence of Cd(NO3)2.4H2O in equimolar ratios is reported. Resulting complex was characterized by
IR spectroscopy, elemental analysis and mass spectroscopy. The result of mass spectroscopy shows
that this is a dinuclear complex.
Keywords: Schiff base; Macrocyclic complex; Cd(II) complex; dinuclear
P-246
Synthesis and characterization of the mononuclear and homodinuclear La(III)
complexes
a
Reza Golbedaghi,a Somaye Moradi,b Sadegh Salehzadeh,b,*
Department of Chemistry, Payame Noor University (PNU), Iran
b
There are a few reports on structural determinations of bimetallic complexes assembling two metal
ions. Most of them are heterodinuclear Ln-Ln' or Ln-M complexes. In this work we report the
synthesis of mononuclear and homodinuclear complexes from reaction La (III) ion with tripodal
Schiff base ligand. Homodinuclear complex with the formulation [LaL]2, was prepared from
thereaction of La(III) with H3L in the presence of base (NEt3). This homodinuclear complex contains
two lanthanum ions, each of which is coordinated by a triply deprotonated N4O3 heptadentate
ligand. Although the [LaL]2 complexes are well known in coordination chemistry but , in the best of
our knowledge, the present [LaL]2 complex is first example of a homodinuclear complex, which is
derived from a tripodal potentially heptadentate (N4O3) Schiff base ligand. Mononuclear complex
with the formulation [LaL] was prepared by the template condensation. The result of IR, accurate
mass spectra, elemental Analysis, 1H and 13C NMR were confirmed the synthesis of the both
complexes.
Keywords: Lanthanum ion, Tripodal Schiff base ligands, Homodinuclear complex, Mass
spectrometry
156
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P-247
A Mass spectrometry study on reactivity of four Salicylaldehyde derivatives with tris (2aminoethyl)amine and formation of symmetrical and asymmetrical tripodal ligands
Reza Golbedaghi,a Somaye Moradi,b Sadegh Salehzadeh,b,* Allan G. Blackmanc
a
b
c
Department of Chemistry, University of Otago, P. O. Box 56, Dunedin, New Zealand
The synthesis of asymmetric tripodal ligands from the Schiff base condensation of symmetric
polyamines with different aldehydes is a challeng. In this work the formation of a set of symmetrical
and asymmetrical ligands from the condensation reaction of different aldehydes derived from
salicylaldehyde with tripodal tetraamine ligand tris(2-aminoethyl)amine (tren) were investigated by
mass spectrometry. Obviously the amount of formation of each product depends on the reactivity of
the aldehyde involve in the Schiff base condensation. In order to study the reactivity of aldehydes
with tren two different procedures were considered for Schiff base condensation. The results show
that the reactivity of the studied aldehydes with tren is as D>A>B>C.
Keywords: tris (2-aminoethyl)amine, salicylaldehyde, Schiff base ligand, reactivity, mass spectromet
P-248
Synthesis and characterization of two new binuclear Cd(II) macrocyclic Schiff base
complex
a
R. Golbedaghi *a S. Salehzadeh b and R. Azadbakht a
b
([email protected])
Macrocyclic and macroacyclic compounds have attracted increasing interest owing to their role in
the understanding of molecular processes occurring in biochemistry, material science, catalysis,
encapsulation, activation, transport and separation phenomena, hydrometallurgy, etc. In this work
we report the synthesis and characterization of two binuclear macrocyclic Schiff base complex of
Cd(II). [2+2] cyclocondensation of L22py = N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,2-diaminoethane
and L33py = [N-(2-pyridylmethyl)-N-(3-aminopropyl)-1,3-diaminopropane}], and 2,6-diformyl-4methylphenol, dfp, in the presence of Cd(NO3)2.4H2O in equimolar ratios gave two new macrocylclic
complexes. Resulting complexes were characterized by IR spectroscopy, elemental analysis and
mass spectroscopy. The results of mass spectra show that both of above complexes are binuclear
and probably phenolic oxygen has been brideged between two metal central ions.
Keywords: Schiff base; Macrocyclic complex; Cd(II) complex; binuclear
A)
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P-249
Cd(II) complexes of two N4O2 macrocyclic Schiff base ligand
a
R. Golbedaghi*a R. Azadbakhta, B. Jalehb
b
Department of physics, Bu-Ali Sina University, Hamedan, Iran
([email protected])
In recent years, there has been an increasing interest in the preparation and characterization of
macrocyclic ligands containing pendant arms, due to their coordination and structural properties.
The cyclocondensation reaction of N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,2-diaminoethane, L22py,
with 2-[4-(2-formylphenoxy)butoxy]benzaldehyde and L23py = N-(2-pyridylmethyl)-N-(3aminopropyl)-1,3-diaminopropane with 2-[2-(2-formylphenoxy)Ethoxy]benzaldehyde in the
presence of equimolar amounts of Cd(II) metal ion is reported. The resulting compounds
[CdL1(NO3)]ClO4 (1), and [CdL1Cl]ClO4 (2), were characterized by IR spectroscopy, elemental
analysis and mass spectrometry. The result of mass spectroscopy shows that the nitrate and
chlorides have been coordinated to the metal central ions respectively and the Cd(II) ions are seven
coordinated.
Keywords: Macrocyclic complex; Schiff base; Cd(II)
P-250
X-ray crystal structure of a novel eight coordinate gadolinium(III) Schiff base complex
Reza Golbedaghi,a Somaye Moradi,b Sadegh Salehzadeh,b,* Allan G. Blackmanc
a
b
c
Department of Chemistry, University of Otago, P. O. Box 56, Dunedin, New Zealand
Complexes of lanthanides could be applied in medicine as contrast agents for magnetic resonance
imaging (MRI). We are interested in synthesis and characterization of potentially heptadentate
(N4O3) tripodal Schiff base ligands and corresponding complexes with lanthanide metal ions. In this
work a novel complex was synthesized from the reaction of gadolinium (III) ion with potentially
heptadentate (N4O3) tripodal Schiff base ligand {N [(CH2)2N=CH(2-OH-5-OCH3C6H3)]3}. Resulting
complex was characterized by elemental analysis, IR, and mass spectrometry and also X-ray crystal
structure. The asymmetric unit of this complex consists of two independent unites (A) and (B), each
of which has the Gd ion surrounded by an N4O4 donor set. Indeed, the X-ray crystal structure of
above complex shows that in addition to all donor atoms of the ligand one molecule of H2O is
coordinated to the metal ion.
Keywords: X-ray structure, tripodal ligand, gadolinium, eight-coordinate.
158
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P-251
New Diorganotin(IV) Complexes of ONO-donor Schiff Bases Containing Pyridine
Moiety: Synthesis, Spectroscopic Characterization and Thermal Analysis
R. habibi and T. Sedaghat*
Organotin (IV) complexes have been the subject of interests for some time because of their
commercial applications and biological properties particularly antitumor, antibacterial and
antifungal activity. An interesting development in bioorganotin chemistry is introducing bioactive
ligands such as Schiff bases. Organotin (IV) complexes with Schiff bases present special
pharmacological and antitumor activity and an interesting of structural possibilities. Among these
the organotin (IV) complexes of Schiff bases containing pyridine moiety showed appreciable
antimicrobial activities and lack of genotoxicity. In this research work, the Schiff bases H2L1 and
H2L2 have been prepared by reaction of 2-amino-3-hydroxypyridine with o-vaniline and 2hydroxynaphthaldehyde, respectively. Then new organotin (IV) complexes SnPh2L1, SnMe2L1,
SnBu2L1, SnPh2L2 and SnMe2L2 were synthesized from reaction of SnR2Cl2 (R=ph, Me and Bu) with
corresponding Schiff bases. The synthesized complexes were investigated by elemental analysis,
and IR, 1HNMR and 119Sn NMR spectroscopy. In complexes the Schiff bases are completely
deprotonated and coordinated to tin as tridentate with an ONO-donor set. The coordination
number of tin is five in solution and the pyridine nitrogen atom is not involved in the coordination
to the tin. In view of the wide application of organotin (IV) compounds, study of the thermal
behavior of these compounds is worthwhile. Therefore, thermal decomposition of the synthesized
complexes was studied by thermogravimetry and the Kinetic parameters determined.
Keywords: Organotin, Schiff bases, Thermogravimetry, Pyridine,
P-252
Electronic and Steric Effects on the Reactivity of Mn(III) Salens Catalyzed Oxidation of
Alcohols with Peroxomonosulfate
a
R. Haddad, A. Rezaeifard*, M. Jafarpour
To mimic active intermediates in enzyme-catalyzed oxidation reactions, metalloporphyrin and
metallosalen complexes have been used as model compounds and have been shown to be capable
of catalyzing oxygen atom transfer from oxygen donors to organic substrates. An essential feature
for understanding the mechanism of the oxygenation reaction is the electronic structure of the
active species and how it is affected by the nature of the oxygen source, substituents in the ligand,
medium of the reaction and by coordination of axial ligands. Indeed, knowledge of electronic
structure of the active species is decisive for understanding the nature of the terminal M-O bond
and its reactivity. In this study the catalytic efficiency of various tetradentate Mn (III)-Schiff base
complexes in the oxidation of alcohols to the related aldehydes and ketones using Bu4NHSO5 under
mild conditions were investigated. The presence of an electron-donating group on the phenyl ring
of the benzyl alcohol increased the reactivity of the substrate while electron-withdrawing and bulky
groups on the Schiff base ligands enhanced the catalytic activity of the Mn-catalyst. Also, the size of
the alkyl chain of Schiff base ligand controls the efficiency of Mn-catalyst.
Keywords: Salen, Alcohol, Oxidation, Peroxomonosulfate, Electronic and steric
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P-253
Synthesis and Characterization of 1,4-dinitrosopiperazine and Its Complexes
a
H.Goudarziafshar*, a A. Ghorbani-Choghamarani, a M. Nikoorazm, b H.Keypour and a L. Hadian
Dehkordy
a
b
Faculty of Chemistry, University of Bu-Ali- Sina , Hammadan , Iran
(e-mail:Leila [email protected])
During the past thirty years the synthesis of metal complexes with organic ligands has been a
popular field of experimental work especially in view of the antitumor action that some platinum
complexes exhibit.Besides the platinum complexes, compounds formed between other divalent
matals and pyrimidine or piperazine derivatives are also of interest. N-Nitroso compounds are of
biological interest and are used as ‘transnitrosating agents’. N-Nitrosamines have been prepared by
various approaches such as the reaction of amines by NaNO2 and an acid, like the method that we
use to produce the ligand in this study. A series of metal binary complexes were synthesized from
the ratio of 2:1 amounts of ligand and metal ions (Cd(II), Mn(II), Cu(II)), (ML2). All of these
complexes have been characterized by IR spectra, elemental analysis and in the case Cd (II)
complex by 1H and 13C NMR and FAB-Mass spectroscopy.
Keywords: N-Nitrosation, NaNO2, Binary complex, 1,4-dinitrosopiperazine
P-254
Removal of G. R.Blue from Dye Wastewater Using pin wood dust by Adsorption
Saeid hafezi*
Islamic Azad University- gachsaran Branch, E-mail: saeid hafezi.removal @gmail.com
Wastewater from textile industry contains various contaminants such as dyes, surfactants and
heavy metals. Textile dyes have synthetic origin and complex aromatic molecular structures that
make them difficult to biodegrade when discharged in the ecosystem. In this research a new
efficient adsorbent of dyes is used. Thus, adsorption of some textile dyes from aqueous solution by
using an industrial waste lignocelluloses product is studied. Pin wood dust was used as an
adsorbent for the removal of G R.Blue dye from an aqueous solution. Effect of various parameters
such as agitation time, pH, temperature and adsorbent dosage has been investigated in the study.
Keywords: Wastewater, pin wood sawdust, G. R.Blue dye, Adsorption
160
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P-255
Removal of reactive orange 12 dye from a textile effluent by adsoroption on rice husk
Saeid hafezia*, mehrnosh kianib
Islamic Azad University- gachsaran Branch, E-mail: saeid hafezi.removal @gmail.com
Many industries in Iran discharge untreated or partially treated wastewater on land or in natural
streams causing pollution to surface water, ground water and the soil. The colour in the water
bodies even in small concentration is easily detectable and lead to inhibitory effect on the process
of photosynthesis and thus affecting the aquatic ecosystem. RICE HUSK was used as an adsorbent
for the removal of reactive orange 12 (R.O.12) dye from an aqueous solution. The studies were
carried out under various experimental conditions such as agitation time, dye concentration,
adsorption dose, pH and temperature to assess the potentiality of RICE HUSK for the removal of
(R.O.12) dye from wastewater. A greater percentage of dye removal was observed with decrease in
the initial concentration of dye and increase in amount of adsorbent.
Keywords: wastewater, RICE HUSK, REACTIVE ORANGE 12, Removal
P-256
Oxidation of Sulfide using Vanadyl Porphyrin: Catalyst Optimization by Experimental
Design Methodology and Computational Study by Density Functional Theory
M. M. Haghdoost, M. Bagherzadeh*
Department of Chemistry, Sharif University of Technology, Iran, Tehran
The selective oxidation of sulfides to sulfoxides is of interest because of the importance of
sulfoxides as synthetic intermediates in organic synthesis. A range of sulfides can be selectively
oxidized to the corresponding sulfoxides in good yields using catalytic quantities of vanadyl
complexes.1 Vanadium oxo tetraphenylporphyrin VO(TPP) catalyst is successfully applied in the
selective oxidation of various sulfides to sulfoxides with urea hydrogen peroxide as oxidant under
mild reaction conditions in excellent yield and selectivity. Several parameters have been tested for
their impact on catalytic performance, measured by the turnover number (TON) and selectivity,
using a surface response methodology for the optimization of the process.2 Structure of the
complex was determined by the density functional theory method B3LYP/DGTZVP basis set. The
optimized geometric bond lengths and bond angles of the complex are in well agreement with the
experimental data.3 Mechanism of sulfide oxidation with VO(TPP) catalyst also has been studied
theorically using the DFT, suggests oxidation of sulfide RRS to sulfoxide RRS=O is carried out by a
(TPP)VO(OOH) intermediate.
Keywords: Vanadyl Porphyrin, Sulfide oxidation, Experimental Design, DFT Study.
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161
P-257
Synthesis of Vanadyl(V)-tetraphenylporphyrin Complex and it’s Application to the
Selective Oxidation of Cyclohexene with Molecular Oxygen: An Experimental
and Computational Study
M. M. Haghdoost, M. Bagherzadeh*
Department of Chemistry, Sharif University of Technology, Tehran, Iran
The activation of dioxygen by metal complexes is a long sought goal in the field of catalysis, and
there are numerous examples in the literature on catalytic aerobic oxidations with different
complex. Recently, the number of applications of Vanadyl (V=O) complexes in catalysis has widely
expanded. In this study, new vanadyl(V)-tetraphenylporphyrin has been synthesized by adding
acetonitrile solution of cerium ammonium nitrate to acetonitrile solution of V(IV)tetraphenylporphyrin. The prepared complex has been characterized by IR, UV-Vis, NMR
spectroscopy and micro analysis. The vanadyl(V) complex showed excellent catalytic activity and
selectivity towards oxidation of cyclohexene using molecular oxygen.
The catalytic oxidative
system selectively oxidizes cyclohexene to 2-cyclohexene -1-one. In the other hand, with urea
hydrogen peroxide (UHP) and tert-butyl hydroperoxide (TBHP) as a oxidant, vanadyl(V)tetraphenylporphyrin don’t show any catalytic activity to this reaction. Structure of VO(TPP)Cl has
been determined with density functional theory, DGTZVP basis sets. Computational study also
showed the oxidation reaction is proceeding through a radicaloid intermediate.
Keywords: Selective epoxidation, Molecular Oxygen, Vanadyl Complexes, Tetraphenylporphyrin,
DFT.
P-258
Synthesis, Characterized and Catalytic behavior of two novel Heterodinuclear
Complexes of Mn,Co
R. Hajializade, A. R. Rezvani*
chemistry Department, university of sistan & baloochestan, Zahedan, Iran, P. O. Box 98135-674
*Email:[email protected]
In this study, dipic2- was used for synthesis of the new dinucler complexes of type
[Mn(H2O)6][Co(dipic)2] (1) and [Mn(bpy)2][Co(dipic)2] (2). The complex (1) was prepared by
mixture of the anaionic complex, [Co(dipic)2]2- and Mn(NO3).4H2O in water as a solvent. The
complex (2) was synthesized by addition of the water solution of cathaionic complex, [Mn(bpy)3]2+
to anaionic complex,[Co(dipi)2]2- complex. These cathaionic-anaionic complexes have been purified
and crystallized by slow evaporation of their water solution. They are fully characterized by FT-IR,
UV-Vis spectroscopy and elemental analysis. The FT-IR spectrum of the dipic ligand shows a strong
band around 1700cm-1 assignable to ν(c=o) of COO-1 moiety. In these complexes, this band was
shifted to lower frequency. This indicates coordination of the dipic ligand to metal ion. The
electronic spectrum of these complexes in H2O shows intense bands at UV-Vis region which are
assigned to π
π* and ligand to metal charge transfer (LMCT). The cathaionic-anaionic complexes
have potential application as hetrogen catalysts in fischer-tropsch synthesis. They were obtained
from addition of silica-gel as supported to complexes solution and left to dry in air. The catalytic
activities of the synthesized catalysts were examined in fischer-tropsch synthesis.
Keywords: Mn-Co, Hetrodinuclear complex, Pyridine-2,6-dicarboxylic acid, catalyst
162
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P-259
The Synthesis and Characterized Novel Hetrobimetallic Complexes of Mn,Co with
Thiocyanat Ligand and Their Application
R. Hajializade, A. R. Rezvani*
*Email:[email protected]
We in this present report herein the easy self-assembly synthesis and full characterization of new
heterodinuclear Mn/Co water-soluble and air stable compounds of general formula
[Mn(H2O)6]3[Co(NCS)6]2 (1) and [Co(H2O)6]2[Mn(NCS)6]3 (2) have been easily prepared by selfassembly of the corresponding metal(II) nitrates with SCN in water solution at room temperature.
The bimetallic complex (1) was synthesized by reaction of Mn(NO3).4H2O with anaionic complex,
[Co(NCS)6]3-. The complex (2) was prepared by a similar method to that for (1). These cathaionicanaionic complexes have been characterized by FT-IR, UV/Vis, atomic absorption spectroscopies
and elemental analysis. The FT-IR spectra of these complexes show two vibration frequency at
2049 cm-1 and 722 cm-1 in which assigned to SCN bond and also shows set of viberation due to the
aqua ligands. These complexes display multiple electronic absorption bands in the 200–800 nm
range in H2O solution which are assigned to MLCT and ligand center transition. The cathaionicanaionic complexes have potential application as a hetrogen catalysts in fischer-tropsch synthesis.
They were obtained from addition of silica-gel as a support to complexes solution and left to dry in
air. The catalytic activities of the synthesized catalysts were examined in fischer-tropsch synthesis.
Keywords: Hetrobimetallic complex, Self-assembly, Thiocyanat ligand, Mn-Co metals
P-260
Preparation and Characterization of Lanthanide Modified Nano-catalysts for Methanol
to Propylene Conversion
a
T.Hajiashrafia, A. Nemati Kharata*.
The evaluation of small-pore molecular sieves as catalysts for the conversion of methanol to light
olefins (MTO) has shown that SAPO-34 exhibits the best performance based on catalyst life,
selectivity to C2-C4 olefins, minimum paraffinic and aromatic byproducts and catalyst stability and
regenerability. SAPO-34 molecular sieves can be selectively formed with hydrothermal methods
irrespective of the acidity or the types of the templates. In this work, Silicoaluminophosphate
(SAPO)-34 molecular sieves modified with internal transition metals such as Praseodymium,
Neodymium, Samarium and Cerium were investigated for their activity, selectivity, and lifetime in
the methanol to olefins (MTO) reaction and compared with that of unmodified SAPO-34. These
catalysts increase propylene selectivity. The structure of synthesized catalysts has been
characterized with several methods such as FT-IR, TGA, SEM, BET and XRD. Results of catalytic
activity for conversion of methanol to olefins illustrate that Ce2O3-Sapo-34 has the highest activity
and selectivity to ethylene and propylene. By rapid crystallization method, the metal-impregnated
crystals having a high crystallinity and a sharp distribution in particle size were obtained. These
catalysts were shown increase propylene selectivity in (MTO) reaction.
Keywords: SAPO-34; MTO; Propylene selectivity; Lanthanides; Nanocatalysts.
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P-261
Complexation of phenolic-amino acid ligands by La3+, Fe3+, Co2+ in a mixed system
solvent
H. Hajibabaei, B. Ghanbaria,*
a Department of Chemistry, Sharif University of Technology, Tehran, Iran
[email protected]
In recent years, there has been an increased interest of the lanthanide complexes. owing to the
unique properties of the lanthanide ions, lanthanides have often been effectively employed as
active Ca2+ and Mg2+ substitutes in many metalloproteins, as chiral NMR shift reagents, MRI
contrast agents, and also luminescent probes of metal binding in biological systems. In this study,
some new and effective phenolic-amino acid ligands has been designed, synthesized and
characterized on the basis of elemental and spectral data. The interest in this study of these ligands
arouse from their tendency to form chelates with transition metals, lanthanides and mane group
metals. Generally, these ligands can be considered as modified amino acids with two phenol
substituent. The determination of the ionization constant and chelating properties exhibited by a
series of derivatives of these type ligands toward La3+, Fe3+, Co2+ ions were studied
potentiometrically. The order of stability of complexes in terms of the amino acid is investigated and
discussed. As a general consideration, all of the titration curves showed that, complex formation
proceeds as well as raising pH.
Keyword: Amino acid, Phenolic group, Chelating ligand, Stability constant, Dissociation constant
P-262
Synthesis, characterization and application of new Phenolic-amino acid ligands as
chelating agents for LSCF membrane
a
H. Hajibabaei, B. Ghanbaria,*
[email protected]
The oxygen permeable perovskite have the general formula of ABO3 in which A composed of rare
and alkaline earth metal ions and B is a transition metal ion. The best discovered perovskite type
membrane for oxygen production and oxidation reaction is La1-xSrxCo1-yFey. Our research focused on
the more reliable complexation route among the other routes that previously have been reported
for ceramic membrane synthesis. Most important step in this synthesis route is the power of
complexation between metal ions and chelating agents. Practically, the common chelating agents
that were used are as EDTA, oxalate, citrate ions as well as amino acids such as glycine. In this
study, some effective phenolic-amino acid chelating agents were designed and synthesized. Then,
the chelating power of these ligands was traced from their solution up to the solid state. The
comparison between XRD patterns for the membranes prepared by glycin (as clelating agent) with
that prepared by the new phenolic-glycine derivative showed that the improved complexation
applying the latter cases. The effect of the better complexation for the newly-prepared phenolic
amino acid ligand in comparison to glycine as ligand. The formation constants for these ligands with
the LSCF cations (as Lanthanum, strontium, cobalt, ferrum) also confirmed on their comparable
degree of comlexations to the EDTA ones.
Keywords: Perovskite, Ceramic membrane, Oxygen permeation, Chelating agent, LSCF
164
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P-263
Methyleneblue Chlorochromate [C16H18N3SCl](CrO3Cl)3, [MBCC] a New Reagent For
Oxidation Organic Substrate
M. HAJIGHAHRAMANIa, S. GHAMMAMYb*, K. MEHRANIa, Z. MEMARZADEHa, T. BANIBAIRAMIa
a
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Ardabil,
Iran, young researchers club (Ardabil branch.) Iran
a
( E-mail: [email protected] )
b
Department of Chemistry, Faculty of Science, Imam Khomeini International University,
Ghazvin, Iran,
b
(E-mail: [email protected] or [email protected])
The new mild chromium (VI) oxidizing agent, Methyleneblue Chlorochromate (VI), (MBCC), was
prepared and characterized. This compound is a new and efficient reagent for the oxidation of
primary and secondary alcohols to their corresponding carbonyl compounds in dichloromethane at
ambient temperature. This is obtained with relatively short reaction times and high yields. The
structure of the [MBCC] studied by variable temperature IR, UV/Visible spectrometer the normal
coordinate analysis.
Keywords: Oxidant; Chromium (VI) reagent; Methyleneblue Chlorochromate; Oxidation;
Organic substrates.
P-264
Synthesis and Characterization of New Ditrialkylammonium
sulfatotrioxochromates,[R3NH]2CrO3SO4,(R=Me, Et, n-Pr, n-Bu)
M. Hajighahramaniaa, R. Zamanpooraa, S. Ghammamy b,*, K. Mehraniaa, T. Banibairamiaa
Department of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Ardabil,
Iran, young researchers club (Ardabil branch.) Iran.
a
(E-mail: [email protected] )
b,*
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Ghazvin
00b
(E-mail: [email protected] or [email protected])
a
The new mild chromium (VI) oxidizing agents, Trialkylammonium sulfatotrioxochromates (TriRASC),
was prepared and characterized. These reagents are suitable for oxidizing various primary and
secondary alcohols to their corresponding carbonyl compounds and anthracene to antraquinone.
Orange solids (TriRASC), is easily synthesized by the reaction of chromium(VI) oxide:
Trialkylammonium salt: in 1:1 molar ratios and sufficient sulfuric acid. These reagents are versatile
reagents for the effective and selective oxidation of organic substrates, in particular for alcohols,
under mild conditions.
Keywords: Chromium
substrate, Alcohols
(VI),
Trialkylammonium
sulfatotrioxochromates,
Oxidation,
Organic
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P-265
Synthesis and characterization of complexes of different Ni2+ salts with bi and
tridentate O and N donor Schiff base ligands
b
N. Hajizadeha , B. Shaabanib,* , E.farajzadehc , F.khosravic ,S.baghbanic,
E.nikjooc,R.shafieezadehc,M.khan soltanic
a
young researchers club, Islamic Azad University Ardabil Branch, Ardabil, Iran
c
Department of chemistry, Islamic Azad University Ardabil Branch, Ardabil, Iran
Schiff base ligands have been in the chemistry catalogue for over 150 years. Not only have they
played a seminal role in the development of modern coordination chemistry, but they can also be
found at key points in the development of inorganic biochemistry, catalysis, medical imaging and
optical materials. Transition metal compounds containing Schiff base ligands have also been of
great interest for many years. These compounds play an important role in the coordination
chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures. In
this work we report the synthesis and characterization of bi and tridentate Schiff-base ligand from
the reaction of 3-hydroxy-2-naphthohydrazied with salicylaldehyde and benzaldehyde, and their
complexes with different salts of Ni2+ cations. The complexes were characterized with IR, Uv/Vis
and conductance measurements.Comparison of spectroscopic results for the ligand and complexes
and also visible absorption spectra for complexes suggest that ligands act as bi and tridentate and
coordinates via and imine nitrogen atoms.
Keywords: Schiff-base, bi and tridentate, Transition metal cations
P-266
Synthesis and characterization of mononuclear Cobalt(III) complexes containing Ndonor tetradentate Schiff-base ligand Bis (2-Benzoylpyridine)-1, 3- diiminopropane
(pbpd) with anionic and neutral ligands:
a,*
M.Hamami a,*, S.J.Moafia
Department of Chemistry, University of Damghan, Damghan, Iran
Schiff base ligands prepare by condensation reaction between simple amines and formyl functional
groups. The tetradentate Schiff- base (pbpd) ligand was prepared by Propane-1,3-diamine and 2Benzoylpyridine were mixed together and refluxed in dehydrated alcohol for 10 h. The yellow
solution that resulted was concentrated on a steam-bath and dried in vacuo over CaCl2 to a yellow
solid. The mentioned Schiff-base ligand refluxed with Cobalt (II) ion under N2 atmosphere.The
desired [CoII (pbpd)] was reacted with monodentate amin ligands (pipiridine and derivatives) while
air was bubbled into the solution for 3h. Then the synthesized [CoIII (pbpd) x2 ] reacted with the
anionic ligand: SCN-. And air was bubbled for further 0.5 hour.The brown solid was recrystallized
from acetone / n-hexane (2:1) solution. In this procedure anation reaction is occurred as one of the
axial ligands replaced by anionic ligand groups. The synthesized where confirmed by 1H,13 C NMR,
FT-IR and UV-Vis-spectroscopies. The effect of axial ligands on Cobalt (II) oxidation and the
geometry of the synthesized complexes was investigated by spectral characterization.
Keywords: Schiff-base, Cobalt (III) complexes, , pbpd, 1HNMR
166
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P-267
Controllable Synthesis of ZnO Flower-like By Microwave Irradiation
N. F .Hamedania, A.R. Mahjoub*a, A. A. khodadadib, Y. Mortazaviband F.Farzanehc
a
Department of Chemistry, Tarbiat Modares University, Tehran, Iran.
b
School of Chemical Engineering, University of Tehran, Tehran, Iran.
c
Department of chemistry, University of Alzahra, Tehran, Iran
Zinc oxide is a direct band gap semiconductor with a room temperature wide band gap of 3.37 eV
and a large excitonic (electron–hole) binding energy of 60 meV. To day, Microwave irradiation as
heating method has found a number of applications in chemistry. Compared to conventional
methods, the microwave synthesis has the advantages such as much rapid reaction and lower
energy consumption. In this work we report a simple and fast method for the preparation of novel
ZnO flower-like by using microwave irradiation. The samples are characterized by XRD, SEM and
FTIR Spectroscopy. It was found that this method is fast, mild and environmentally friendly rout to
produced ZnO Flower-like nano structures.
Keywords: Microwave irradiation, ZnO, Flower-Like, Nanocrystals.
P-268
Immobilization of Biomimetic Amino acid Copper Complexes for Epoxidation of Olefins
L. Hamidi pour, F. Farzaneh*
Department of Chemistry, University of Alzahra, Vanak, Tehran, Iran
[email protected]
Amino acids as protein constitutes are small molecules with various functional groups. L-histidine
((s)-2-amino-3(4-imidazolyl) propionic acid) is a very strong metal-coordinating ligand. In this
study, copper complexes with L-histidine were prepared and then encapsulated in nanoreactors of
Al-MCM-41. This novel encapsulation procedure, which involves building a mesoporous (host)
around preformed and structurally defined amino acids copper complexes (guest), results in the
generation of isolated single-site for catalytic epoxidations. The obtained results indicate that
Cu(His)2 complex was formed by coordination to the nitrogen atoms of the amino group and
oxygen atom of the carboxylate group. The hydrophobic/hydrophilic nature of the Al-MCM-41
coupled with activity of metal complexes generate high active and selective heterogeneous catalyst
for epoxidation of olefines such as cyclohexen, trans stilben, styren and norbornen with 60% to
90%-conversion and 30% -99%-selectivity. The pore volume, surface area and pore diameter of AlMCM-41 were decreased after immobilization of copper amino acid complexes. The prepared
catalysts were characterized by powder X-ray diffraction (XRD), nitrogen adsorption desorption,
FTIR and UV-Vis techniques and epoxidation products were analyzed by GC and GC-Mass.
Keywords: Copper histidine complex, Immobilization, Alkenes, Al-MCM-41, Epoxidation
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P-269
Heteropoly acid as an Efficient Catalyst for Synthesis of 2-Aryl benzthiazoline,
benzthiazol and benzimidazole
H.Hammadia*, M. Khoobib, A. Shafieec
Department of Chemistry, Chamran University, Ahvaz 61357-4-3169, Iran
b
Department of Chemistry, Zanjan University, PO Box 45195-313, Zanjan, Iran
Faculty of Pharmacy, and Pharmaceutical Sciences Research Center, Tehran University of Medical
Sciences, Tehran 14174, Iran
a
c
Heteropolyacid compounds (HPAs) with Keggin-structure are polynuclear complexes principally
constituted by molybdenum or tungsten as polyatoms, and phosphorus and silicon as central atoms
or heteroatoms. They operate either as multielectron oxidants or strong acids, with an acid strength
higher than that of classical acids.On other hand benzthiazolines, benzthiazoles and benzimidazoles
derivatives have received considerable attention in organic synthesis and pharmaceutical chemistry.
These heterocycles have varied pharmacological activities such as antibiotic, anticancer, antiviral,
antifungal, antimicrobial and antiparkinson, properties. Thus the reaction of benzaldehyde and
aceteophenon derivatives with O-aminophenol or O-phenylene diamine in the presence of catalytic
amount of heteropoly acid in free solvent was performed to produce the related benzimidazole,
benzthiazole and benzthiazoline. We have found that the reaction proceed without any oxidizing
agent that used in previous reports 33 in excellent yields and heteropoly acid has played double
activity that catalyzed the reaction and oxidized to benzthiazole.
Keywords: Heteropoly acid, Catalyst, Benzimidazole, Benzthiazole, Benzthiazoline
P-270
One-pot, Eco-friendly and Efficient Synthesis of 3-Benzthiazole and 3-Benzthiazoline
Coumarin Derivatives Catalyzed by Heteropoly Acids using Microwave
H.Hammadia*, M. Khoobib, A. Shafieec
Department of Chemistry, Chamran University, Ahvaz 61357-4-3169, Iran
b
Department of Chemistry, Zanjan University, PO Box 45195-313, Zanjan, Iran
Faculty of Pharmacy, and Pharmaceutical Sciences Research Center, Tehran University of Medical
Sciences, Tehran 14174, Iran
a
c
In this paper heteropoly acids (H3PW12O40 and H3PMo12O40) perform as an efficient Catalyst for the
synthesis of 3-benzthiazole Coumarin and 3-benzthiazoline Coumarin from O-aminothiophenol with
3-acetly and 3-cyano chromen 2-one in excellent isolated yields (87-98%) under microwave
irradiation. This study showed remarkable advantages that offered this method for synthesis of new
class of chromen derivatives for instance it can be mentioned inexpensive and easily available
catalyst, a simple procedure, mild conditions, and good to excellent yields of products. We have
been prompted to synthesize new, possibly more potent, pharmacologically active compounds. We
decided to combine the coumarinic system with the above named groups of compounds in hope
that the resulting novel substituted coumarins would be biologically active (investigation of the
pharmacological activity of the synthesized compounds are currently in progress). The procedure
was simple and the entire product was filtered as a solid and purified with recrystalization in
ethanol. This procedure will offer an easy access to substituted coumarins with different
substitution patterns in high to excellent yields.
Keywords: Please give 4-6 single or double words separated by comma. Start each word by
capital letter.
168
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P-271
Synthesis and characterization of luIII Doped Sb2Se3 Nano materials via co-reduction
method and their optical properties
Y.Hanifehpour Firouzsalari, A. Alemi*, Sh.Khademinia, E.Gavidel
During the past few years the synthesis process and spectroscopic properties of lanthanide-doped
nanoparticles have attracted considerable attention, since they are considered as potentially useful
active components in lamps and displays, lasers, and new optoelectronic devices. Luminescent Sb2xLuxSe3 nano particles were prepared by a hydrothermal co-reduction method. Grey selenium
(0.237 g, 1 mmol), and NaOH (0.6 g, 15 mmol) were added to distilled water (60 mL) and stirred
well for 10 min at room temperature. Afterwards, hydrazine hydroxide (2 mL) and SbCl3 and Lu2O3
with different molar ratios were added and the mixture was transferred to a 100 mL Teflon-lined
autoclave. The autoclave was sealed, maintained at 180 °C for 48 h and then cooled to room
temperature. The black precipitate obtained was filtered and washed with ethanol and water. XRD
patterns indicate that the Sb2-xLuxSe3 crystals with 0-8 mol-% Lu3+ are isostructural with Sb2Se3.
SEM shows morphology changes upon doping of Lu3+ ions into antimony sites from separate nanorods to nano-particles. UV/Vis spectra show that an increasing concentration of Lu3+ ions increases
the intensity of some peaks in the absorption spectrum of Sb2Se3. Also, there is a red shift in the
Sb2Se3 absorption peaks upon increased Lu3+ concentration.
Keywords: Semiconductor, Antimony Selenide, Nanomaterials, Co-reduction, Luminescent.
P-272
Synthesis and characterization of Gd+3 doped Sb2S3 Nanorods via hydrothermal route
and their optical properties
Y.Hanifehpour Firouzsalaria, A. Alemia,*, R. Beheshti Nahandb
b
Department of Medicinal Chemistry, Faculty of Pharmacy, University of Tehran, Iran
a
Antimony sulfide, a layer-structured direct band gap semiconductor with orthorhombic crystal
structure, is an important semiconductor with high photo sensitivity and high thermoelectric power .
Luminescent GdxSb2-xS3 micro crystals were prepared by a hydrothermal method. Elemental sulfur
(0.032 g, 1 mmol), and NaOH (0.6 g, 15 mmol) were added to distilled water (60 mL) and stirred
well for 10 min at room temperature. Afterwards, hydrazine hydroxide (2 mL) and SbCl3 and GdCl3
with different molar ratios were added and the mixture was transferred to a 100 mL Teflon-lined
autoclave. The autoclave was sealed, maintained at 180 °C for 48 h and then cooled to room
temperature. The black precipitate obtained was filtered and washed with ethanol and water. The
powder X-ray diffraction pattern shows the GdxSb2-xS3 crystals belong to the orthorhombic phase
with calculated lattice parameters a=1.120nm, b=1.128nm and c=0.383nm. SEM shows no
morphology changes upon doping of Gd3+ ions into antimony sites .UV/Vis spectra show that an
increasing concentration of Gd3+ ions increases the intensity of some peaks in the absorption
spectrum of Sb2S3. Also, there is a red shift in the Sb2S3 absorption peaks upon increased Gd3+
concentration and photoluminescence spectra show this shift, respectively.
Keywords: Antimony sulfide, Nanorods, Luminescent, Hydrothermal, Semiconductor.
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169
P-273
Hydrothermal Synthesis of YbIII Doped Sb2Te3 Nano crystals and their optical Properties
Younes Hanifehpour Firouzsalaria, Abdolali Alemia,*, Reza Beheshti Nahandb
b
Department of Medicinal Chemistry, Faculty of Pharmacy, University of Tehran, Iran
*E-mail: [email protected]
a
Luminescent Sb2-xYbxTe3 nano crystals were prepared by a hydrothermal co-reduction method.
Tellurium (1 mmol), and NaOH (0.6g) were added to distilled water (60 mL), and then NaBH4 (0.5g)
and SbCl3 and Yb2O3 with stoichiometric molar ratio were added and the mixture was transferred to
a 100 mL Teflon-lined autoclave. The autoclave was sealed, maintained at 180 °C for 48 h and then
cooled to room temperature. The black precipitate obtained was filtered and washed with ethanol
and water. The powder X-ray diffraction pattern shows the Sb2-xYbxTe3 crystals belong to the
orthorhombic phase with calculated lattice parameters a=1.163nm, b=1.180nm and
c=0.396nm.XRD patterns indicate that the Sb2-xYbxTe3 crystals with 0-6 mol-% Yb3+ are
isostructural with Sb2Te3. SEM shows morphology changes upon doping of Yb3+ ions into antimony
sites from separate nano-rods to nano-crystals .There is a red shift in the Sb2Te3
photoluminescence spectra. Also, there is a red shift in the Sb2Te3 absorption peaks upon increased
Yb3+ concentration. UV/Vis spectra show that an increasing concentration of Yb3+ ions increases the
intensity of some peaks in the absorption spectrum of Sb2Te3.
Keywords: Antimony Telluride, Thermoelectric, Nanocrystals, Luminescent, Hydrothermal.
P-274
Electrochemical Synthesis of Zn(II) and Cu(II) Schiff Base Complexes
Z. Harandizadeha, V. Mirkhania*, D. Nematollahib, S. Tangestaninejada, M. Moghadama, E. Shamsa,
I. Mohammadpoor-Baltorka, A. Rostami-Vartoonia
a
Department of Chemistry, University of Isfahan, Isfahan, Iran
b
Department of Chemistry, Faculty of Sciences, Bu-Ali-Sina University, Hamadan, Iran
Many complexes of the Schiff base ligands with different metal cations have been recognized as
powerful catalysts in a great number of chemical reactions such as oxidation, amidation and
aziridination of hydrocarbons, epoxidation and polymerization of olefins, alkynylation of aldehydes,
reduction of ketones to alcohols and carbonylation of alcohols. Electrochemical procedures have
been widely used for the synthesis of metal complexes, especially in cases where the organic
ligands containing weak acidity groups. For the preparation of complexes with N2O2 tetradentate
Schiff bases in this work, an acetonitrile solution of ligand, containing a few mg of Bu4NClO4 (TBAP)
as a current carrier, was electrolyzed using a platinum wire as the cathode and a metal plate (Zn or
Cu) as the sacrificial anode. The current was maintained at 15 mA for 2 h. The applied voltages
allowed sufficient current flow for smooth dissolution of the metal. Characterization of synthesized
complexes was carried out with FTIR, NMR, UV–Vis spectroscopy and elemental analysis. The
conditions employed in this experimental methodology have proved suitable for deprotonating of
hydroxyl functions and thus it provides an easy and inexpensive synthetic procedure whereby
complexes may be formed in the absence of external coordinating species.
Keywords: Electrochemical Synthesis, Schiff Base, Sacrificial Anode
170
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P-275
Photocatalytic degradation of pararosaniline in aquatic system using semiconductor
oxides in various pH
J. Hasanalian and M. Montazerozohori*
Department of Chemistry, Yasouj University, Yasouj, 7591874831, Iran.
(E-mail:[email protected]; [email protected])
It has been documented that between 1–20% of the total world production of dyes is lost during
the dyeing processes and providing major wastewater pollution in wastewaters. There are aromatic
rings in the dye molecular structures which cause these effluents to be toxic and mostly nonbiodegradable; therefore, be coming an important source of environmental pollution. In this regard
and in recent years have been showed that photocatalysis has become a hot topic because it can
completely degrade the organic pollutants into harmless inorganic substances such as CO2 and H2O.
When we arrived to this state, these compounds didn’t have any previous navigate such as toxic
pollutant and etc. harmful if swallowed and may be harmful by inhalation or through skin contact.
Also it is Eye irritant. Therefore degradation study and kinetic parameters seems to be a need for
environmentally friendly chemists. In this work has showed that pararosaniline, an azo dye, can be
highly degraded using TiO2 catalyst and irradiation with a UV lamp. The observed results revealed
that the order of photocatalytic activity for degradation of selected compounds was TiO2 (anatase)
> ZnO ~ TiO2 (rutile). Besides, the influence of catalyst concentration, pH and time of irradiation
were studied. Spectrophotometric methods supported that the titled compound almost completely
decomposed.
Keywords: Photocatalytic, degradation, pararosaniline,TiO2(anatase)
P-276
Synthesis and spectral identification of some new mercury complexes of (E)-2-(4
(dimethylamino) benzylidene-amino)benzenethiol
J. Hasanalian and M. Montazerozohori*
Department of Chemistry, Yasouj University, Yasouj 75918-74831Iran
(E- mail:[email protected]; [email protected])
The field of Schiff base complexes was fast developing on account of the wide variety of possible
structures for the ligands depending upon the aldehydes and amines. Schiff bases offer versatile
and flexible ligands capable of binding with metal cations to Yield complexes, some of them have
suitable properties for practical applications. Synthesis of these Schiff base complexes is achieved
through the template reaction or transmetallation reactions which are used when the transition
metal cations are ineffective as templates. Thiolic Schiff base are newer compounds among the
family of Schiff base. And therefore their complexes are very rare in the literature. In this project
we wish to report synthesis of some new complexes of mercury (II) ions with a new thiolic ligand of
(E)-2-(4-(dimethylamino)benzylideneamino)benzenethiol. All complexes were characterized by
analytical, spectroscopic, conductivity measurement. FT-IR and NMR spectra of the complexes
exhibit downfield as well as upfield shifts of the coordinated ligand with respect to free once that
shows synthesis of coordination compounds. The suggested structure of the complexes is pseudotetrahedral.
Keywords: Synthesis, Complex, Benzenethiol, Mercury (II).
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171
P-277
Thermal Analysis of Solid State Isomerization of Dinitro and Dinitrito Isomers of
Bis(ethylenediamine)cobalt(III) Complexes.
N.Hasani, A.Eslami*
Linkage isomerism approach is as old as Werner outstanding theory of coordination chemistry. In
spite of this rich background, linkage isomerism is still a subject of great interest for both structural
and biological studies. Several spectral methods have been exploited to follow interconversion of
linkage isomers both in solid and solutions, including IR, UV-Vis, NMR, and XRD. However, the
relative stability and the reactivity of linkage isomers could be directly estimated from thermal data.
So in this study, non-isothermal differential scanning calorimetry (DSC) was utilized to explore
interconversion of trans-[Co(en)2(NO2)2]X and trans-[Co(en)2(ONO)2]X linkage isomers in solid
state. The DSC data allowed us to determine thermodynamic and thermokinetic parameters linkage
isomerization of the interconversion. Both kinetic and thermodynamic results for pure samples could
be obtained by a few runs of DSC experiments within a limited time period, this is a distinguished
advantageous of DSC over spectral methods.
Keywords: Linkage isomers, DSC, Interconversion, Thermal analysis, Nitro and nitrite,
Intramolecular
P-278
Synthesis and characterization of blue inorganic pigment Using chemical co
precipitation and sol gel method
a
Saeedeh Hashemiana, *, Ali Shamsi
Islamic Azad University, Yazd branch, Chemistry department, Iran, Yazd
The nano blue inorganic ceramic pigment of CoAl2O4 was synthesized. The inorganic pigment was
prepared using the chemical co-precipitation and sol-gel methods. The powders were calcined
between 200 to 1200 ºC. Characterization using X-ray powder diffraction, FTIR, diffuse reflectance
spectroscopy using CIE L∗ a∗ b∗ parameter measurement method and transmission electron
microscopy (TEM) is used. The results of XRD showed the spinel phase of CoAl2O4 was form up to
500 ºC at 2θ = 36 and d=2.5. The inorganic blue pigment was formed at cubic system of
crystallography.
Keywords: Blue pigment, inorganic pigment, CoAl2O4, co-percipitation, Sol-gel
172
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P-279
Synthesis and Characterization of Mixed Ligand Complexes of Cu (II) - imidazoloxalate
a
Saeedeh Hashemiana,*, Mahdeeh Zarezadeh
Biological metal ions play key role in the structural organization and activation of certain enzymes,
leading to the synthesis of specific proteins. The ternary complexes play an important role in
biological processes. The complexes of Cu (II) were prepared. The mixed ligand complex involving
oxalate and imidazole had been performed. The prepared complexes are characterized by IR and
UV/Vis spectroscopic methods. The UV–Vis of oxalate complex had bonds at 228 and 295 nm. For
ternary complex of Cu and oxalate and imidazole the absorption band appears at 225 and 269 nm.
The elemental analysis and electro conductivity of complexes also were done. Based on elemental
and spectra data, the complexes of binary and ternary of Cu had formula Na4[Cu(ox)3] and Na2[Cu
(imi) 2(ox)2] respectively. At ternary complex of Cu, the octahedral structure was determined. The
complex of Na2[Cu (imi) 2(ox)2] had two isomer of cis and trans. The oxalate acts and bidentate
ligand.
Key Words: Cu (II),Imidazol, Mixed ligand complexes, Oxalate
P-280
Synthesis and characterization of complexes of guanidine and cysteine with Cu (II) and
Co (II)
a
Saeedeh Hashemiana,*, Elham Sajadeih
The guanidine functionality is found widely in natural products, pharmaceutically active compounds.
Many natural metabolites found in a variety of organisms contain guanidine. Cysteine as Cys is an
α-amino acid with the chemical formula HO2CCH(NH2)CH2SH. It is a non-essential amino acid, which
means that it is biosynthesized in humans. The mixed ligand complexes of Cu2+ and Co2+ ion with
guanidinium and amino acid cysteine were prepared. The structures of complexes were
characterized by elemental analysis(C,H,N), electroconductivty (EC), IR and UV/Vis spectroscopy.
The IR spectra were shown the coordination of both ligands guanidinium and amino acid cysteine
with metals. The electronic spectra data for the complexes were in accordance with an octahedral
structure around the metal ions. The guanidinium acts a nuidentate ligand and cysteine acts as
bidentate ligand.
Keywords: Amino acid, cysteine, Complex, Mixed ligand,
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173
P-281
Stable Aqueous Dispersions of ZnO Nanoparticles by Employing of Aminoclay
Fatemeh Hashemiyan, S. J. Hoseini*
[email protected]
Zinc oxide (ZnO) is an important II-VI semiconductor because of its direct band gap of 3.37 eV and
a large exciton binding energy (60 meV). It has potential applications in solar cells, sensors,
photocatalysis, etc. Many efforts have been made to obtain nearly monodispersed ZnO
nanoparticles simply by hydrolysing zinc acetate in alcohol solutions. Size, shape and luminescent
properties could be readily controlled by capping the surface with dodecylamine (DDA),
trioctylphosphine oxide (TOPO), dodecanethiol, oleic acid, alkoxysilanes or SiO2. These
nanoparticles are generally soluble in organic solvents, such as toluene, hexane or chloroform. ZnO
is an environmentally friendly material, which is desirable for bio-applications such as cancer
detection. However, a water soluble surface is necessary for biological labels. In this work, we have
used an aminoclay, a phyllosilicate family of molecular formula R8Si8Mg6O16(OH)4, where R =
CH2CH2NH2 as the water dispersible support. ZnO nanoparticles were immobilized on exfoliated
aminoclay sheets by carrying out the alkaline hydrolysis of Zn(OAc)2 in the presence of aminoclay.
Immobilization is resulted from strong affinity of nitrogen towards Zn atoms at the surface of the
nanoparticles. In conclusion, water dispersible ZnO-aminoclay nanoparticles were synthesized.
These nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction
(XRD) and IR spectroscopy.
Keywords: ZnO, Nanoparticles, Aminoclay, Stable Dispersion
P-282
Synthesis and Characterization of Cationic-Anionic Complex of Fe (III), Co(III)
M.Hassani , A .R. Rezvani*,H.Saravani
Correspoinding Author :Email:[email protected]
Transition metals in low oxidation states are able to form complexes with many unsaturated organic
ligands. 2,2’-bipyridine is both a σ-donor and a π-acceptor ligand. The lone electron pair of
nitrogen can form a σ-bond with the central atom, while the aromatic system can take part in backbonding. These will stabilize metal ions, especially transition metal ions in low oxidation states. In
this study , the new complex [Fe (bpy )3][Co (SCN )6] (where bpy =2,2 – bipyridine and SCN =
thiocyanate ) was synthesized and characterized by elemental analysis, conductivity measurement,
FT –IR, UV – vis, 1 H-NMR and Atomic Absorption spectroscopy. The IR spectrum of [Fe (bpy)3][Co
(SCN )6] complex depicts several ( CN ) bands at ( 1144 and 1466 Cm -1 ) which are attributed to
the presence of bpy group as ligand. Also the absorptions in the (2065 and 3253 Cm-1) region,
corresponding to theν(C ΞN)) modes of the thiocyanate ligand in IR spectrum. The UV–Vis spectrum
was obtained for the aqueous solution of this complex. The intense absorption bands at 204 nm
and 262 nm is due to
* transitions within the pyridine and thiocyanate moiety respectively.
While the absorption band observed at 507 nm is due to the d d transition of Fe (III) metal ion .
Keywords: Cationic-Anionic Complex, Bpy , Thiocyanate, Conductivity measurement.
174
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P-283
The Synthesis, Characterization of Two New Iron (III) and Cobalt (III) Complexes,
Containing Dipic and bpy as ligands.
M.Hassani , A .R. Rezvani*
Chemistry Department, university of sistan & baluchestan, Zahedan, Iran, P. O. Box 98135-674
Correspoinding Author :Email:[email protected]
In this study , the new [Fe (dipic)2]3[Co (bpy)3]2 (I) and [Fe(bpy)3 ]2[Co (dipic )2]3 (II) complexes
(where dipic =2,6-pyridinedicarboxylic and bpy =2,2' – bipyridine ) were synthesized and
charaterized by spectroscopyic methods (IR , UV –Vis , 1H-NMR , Atomic absorption and Cyclic
Voltametry ). The most characteristic feature of the IR absorption spectra of two compounds (I)
and (II) , is the presence of well identifiable strong and sharp absorption bands , due to asym(C=O )
mode of the dipic ligand .These are positioned at 1704 cm-1 for (1), and 1699 cm-1 for (2) ,
respectively. The complexes (I) and (II) shows the usual absorption bands vibrations of ν(c-N) at
1414 and 1597 Cm-1 of the bpy as ligand, respectively. In (I) complex there are a broad absorption
bands at (2628 and 3069 cm-1) attributed to the (OH) vibrations of water molecules in the crystal.
In contrast the UV/visible spectrum contains absorption at 272 and 281-302 nm due to the
*) and (
*,n
*) transition, that attributed dipic ligand in (I) and (II)
intraligand (
complex respectively. The cyclic voltammogram shows one quasi reversible reduction couples and
one cathodic wave which are assigned to the reduction Fe (III/II) and cobalt at 100mv/s. Existence
of iron and cobalt metal ions in these complexes was confirmed by atomic absorption spectroscopy.
Kywords: Fe – Co Complex, 2,6-pyridinedicarboxylic, 2,2' – bipyridine, UV/visible spectrum.
P-284
The synthesis, characterization and studies of Co (III) and Fe (III) complex with
Dipicolinate ligand.
M.Hassani , A .R. Rezvani*
Chemistry Department, university of sistan & baluchestan, Zahedan, Iran, P. O. Box 98135-674
*Correspoinding Author :Email:[email protected]
Pyridine-2,6-dicarboxylic acid (H2dipic) forms stable chelates with simple metal ions and oxometal
cations and can display widely varying coordination behavior, functioning as a multidentate ligand.
Dipicolinate complexes have been used as electron carriers in some model biological systems as
specific molecular tools in DNA cleavage and as NO scavengers. In this work, it was reported the
synthesis of the [Fe (dipic)2]3 [Co(H2O)6] complex. This complex have been synthesized by
mixture of [Fe(dipic)2](H5O2) and Co (NO3).6H2O and characterized by elemental analysis and
various spectroscopic techniques such as FT – IR and UV – vis . The IR spectrum of the free ligand
(H2dipic) shows a strong band around 1700 cm-1 assignable to ν ( C=O ) of COOH moiety . In this
complex, the band due to ν (COO-) was observed in the region 1637 cm-1. The electronic spectra of
[Fe (dipic)2]3 [Co(H2O)6] complex was obtained in water solution shows two intense bands at UVvis region which are assigned to
and d
of dipic and Fe(III) ion ,
respectively. The Atomic Absorption Spectroscopy (AAS) measurements, verified the presence
of Iron and Cobalt ions in this complex .
Keywords: Fe – Co complex, Dipicolinic acid, Atomic Absorption Spectroscopy, scavengers.
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P-285
Emerging a new biological active CobaltII coordination compound involving salicylic
acid and acridine moieteis: DNA binding and cytotoxicity studies
A. Hassanpoor*, H. Eshtiagh-Hosseini, M.R. Housaindokht and M. Mirzaeia
The field of anticancer metallodrugs is dominated by platinum based compounds and the so-called
“DNA paradigm”, which presumes that the mechanism action of metallodrugs relies on direct DNA
damage. However, in recent years, it has become increasingly evident that several cytotoxic
metallodrugs exert their biological and pharmacological actions through DNA independent
mechanisms. In this paper, a new cobaltII coordination compound was synthesized by using proton
transfer mechanism. Obtained results show that it has successfully interacted with DNA and it binds
to DNA and does not allow the denaturation of double helix. The reaction between CoCl2.2H2O,
Salicylic acid (SalH), and Acridine (Acr) gave a new coordination compound formulated as
(Acr)4[Co(Sal)3].nH2O. The title compound was characterized by elemental analysis, NMR, IR and
UV/vis spectroscopies.
Keywords: Proton transfer compounds, Coordination compounds, Cobalt, Salicylic acid, DNA,
Biological activity.
P-286
Synthesis and characterization of new proton transfer ligand and chromeIII
coordination compound
A. Hassanpoor*, H. Eshtiagh-Hosseini, A. Mousavinezhad, M. Mirzaei
Two new compound with formulas (tataH)2(pzdc).4H2O (1) ( tata = 2,4,6-triamino-1,3,5- triazine,
pzdcH2 = pyrazine-2,3-dicarboxylic acid) and (BH)[Cr(pzdc)2]n (2) were synthesized. The BH ligand
synthesized by the literature method. The products have been characterized by means of elemental
analyses, NMR, and IR spectroscopies. The compound 1 crystallized in the triclinic system, space
group P-1, with a = 7.0200 (14) Å, b = 9.763 (2) Å, c = 15.397 (3) Å, α = 101.06 (3)˚, β= 99.82
(3)˚, γ = 96.98 (3)˚. In the crystal structure, an extensive series of O—H…O, O—H…N, N—H…O
and N—H…N hydrogen bonds generates a three-dimensional framework with the hydrogen bonding
involving most donor and acceptor centers. π-π stacking interactions are also observed between
adjacent triazine rings, with centroid–centroid distances of 3.4994 (8) and 3.5922 (7) Å. Future
efforts have been done to obtain good quality single crystals of compound 2 for better identification
its molecular and crystal structure.
Keywords: Proton transfer ligands, Chrome, Pyrazine-2,3-dicarboxylic acid, Hydrogen bond, X-ray
crystallography.
176
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P-287
Encapsulation of Methoxo-bridged Dinuclear Copper (II) Complexes with 4Pyridinemethanol as Ligand in NaY-Zeolite under Microwave Irradiation
a
F. Hassanvanda,*, S. Amania
Department of Chemistry, University of Arak, Arak, Iran
The use of transition metal complexes encapsulated in to solid supports as heterogeneous catalysts
has very important for ecofriently industrial processes. These materials have been developed with
the objective to perform reactions under milder conditions and with out hazardous wastes. These
new catalysts can easily be separated from the reaction media and reused, as they are quite stable
when compared with the corresponding homogenous counterparts. Among a variety of supports,
zeolites have been often used. To improve the separation of catalyst from the reaction medium and
to increase its active life, various strategies can be employed. One of these strategies is the
encapsulation of the transition metal complexes in zeolites. [Cu (L)2(µ-OCH3)]2Cl2 complex in which
L =4-pyridinemethanol was synthesized and encapsulated in NaY Zeolite under microwave
irradiation. The new material was characterized by chemical analysis, Fourier transform infrared
(FTIR), X-ray diffraction (XRD), diffuse reflectance UV-Vis spectroscopy (DRS).
Keywords: Copper (II) complexes, Dinuclear, NaY Zeolite, Microwave irradiation. Heterogeneous
catalysts.
P-288
Synthesis and Characterization of Six Hydroxo or Alkoxo-bridged Dinuclear Copper (II)
Complexes with 2-Pyridinemethanole, 3-Pyridinemethanol or 4Pyridinemethanol as Ligand
a
The synthesis and characterization of six new dinuclear copper (II) complexes are described. The
compounds have the general formula [Cu(L)(µ-R)]2Cl2, in which L =2-pyridinemethanole, 3pyridinemethanol or 4-pyridinemethanol, R=OCH3- or OH-.The compounds were synthesized in a
one step reaction and characterized by elemental analysis, Fourier transform infrared (FTIR), and
electronic spectra and by room temperature magnetic moments. The compounds exhibit
antiferromagnetic interactions at room temperature. Magnetic properties of a poly nuclear complex
of paramagnetic metal ions are, in general, different from the sum of the magnetic properties of
each metal ion fragment separately. UV- Viz spectra show four absorptions attributed to d-d
transitions of copper, ligand
metal charge transfer and π
π* or n
π* transitions of ligand.
The FT-IR spectra indicate Cu202 ring vibrations.
Keywords: Copper (II) complexes, Dinuclear, Spin-spin interaction, Magnetic property.
IICC12
177
P-289
Synthesis and Characterization of Six Dinuclear Copper (II) Complexes with 2-Amino-5bromopyridineas Ligand
a
The synthesis and characterization of six new dinuclear copper (II) complexes are described. The
compounds havethe general formula [Cu(L)(µ-R)]2X2, in which L=2-Amino-5-bromopyridine, R
=CH3COO-, OC2H5-, OCH3- or OH-,and X =CH3COO-, NO3-, ClO4- or Cl-. The compounds were
synthesized in a one step reaction and
characterized by elemental analysis, Fourier transform
infrared (FTIR), and electronic spectra and by room temperature magnetic moments. The
compounds exhibit antiferromagnetic interactions at room temperature. Magnetic properties of a
poly nuclear complex of paramagnetic metal ions are, in general, different from the sum of the
magnetic properties of each metal ion fragment separately. UV- Viz spectra show four absorptions
attributed to d-d transitions of copper, ligand
metal charge transfer and π
π* or n
π*
transitions of ligand. The FT-IR spectra indicate Cu202 ring vibrations.
Keywords: Copper (II) complexes, Dinuclear, Spin-spin interaction, Magnetic property.
P-290
Surveying thermal behaviour and glass transitin and energy giving behaviour of some
calixarene compound and their complexes with some transition metals and comparing
their energy giving with TNT by DSC
Sanaz Hedayati*a, Ali Hassanzadeh b and Behrooz Shaabanic
Department of Chemistry, Islamic Azad University of Ardabil branch, Ardabil, Iran
b
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Department of Inorganic Chemistry, Faculty of Chemistry, Tabriz University, Tabriz, Iran
a
c
Thermal analysis means calculating physical properties of materials as a function of temperature
while they are affected by controlled thermal program. In this paper we studied Tg by surveyimg
DSC thrmograms of above compounds and we observed at above mentioned compounds have a
peak based on glass transition temperature. For proving the existence of this transition in
compound we enjoyed powdery x-ray diffraction technic. By caring in resulats obtained from x-ray
diffraction patterns and comparing them by resulats obtained from DSC thermograms we observed
that the data of both technic correspond with each other completely. In gained thermograms we
observed that their melting peak in the form of sharp peak and thermal destructive temperature of
synthesized compound is also high so we surveyed energy giving property of the compound by
comparing the destructive temperature of compound in DSC with destructive temperature of
energetic substance TNT and also thermograms obtained from mixing TNT and above mentioned
compound.
Keywords: DSC, XRD, Tg, TNT.
178
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P-291
Synthesis, identification and theoretical study of some new complexes of mercury and
cadmium with a symmetrical Schiff base ligand
B. Heidari1, M. Montazerozohori2*, S. Joohari3, M. Sedighipoor2
Department of Chemistry, Islamic Azad University, Firoozabad Branch , Firoozabad, Iran .
2
Department of Chemistry, Yasouj University, Yasouj, 7591874831 Iran.
3
Department of Chemistry, Islamic Azad University, Yasouj Branch , Yasouj, Iran .
(E- mail: [email protected])
1
The Schiff bases originating from condensation reaction from aldehydes/ketons and amines are a
class of suitable ligands with potential binding to a variety of metal ions to produce Schiff base
complexes. Many attempts were carried out to obtain some symmetric polydentate ligands in order
to synthesize rare coordination number with mercury and cadmium ions because of their ability to
form metal chelates. The aim of the present study is to synthesize and characterize of new several
mercury and cadmium complexes of (N1E, N2E)-N1, N2-bis((E)-2-chlorobenzylidene)
ethylenediamine (L). These complexes were synthesized with drop wise addition of the ligand to
metal salt in methanol/dichloromethane mixture with severe stirring for 3-4h. The general formula
of these complexes are MLX2 wherein M = mercury, cadmium and X = halide. The ligand and
complexes were characterized by physical and spectral data. The structure of ligand and complexes
were optimized using a semi-empirical quantum mechanics method (MM+).
Keywords: Schiff base, Symmetric, 2-chlorobenzaldehyde, Mercury, Cadmium
P-292
Ruthenium (III) chloride hydrate: a suitable catalyst for the synthesis of some new
biscoumarin compounds in a mild and green approach
H. Heidari, K. Tabatabaeian*, M. Mamaghani, N. Mahmoodi
Homogeneous catalysis is becoming one of the most significant fields for organic chemists,
industrial chemists, and academia. Transition metals and especially ruthenium compounds are
favorable materials having useful characteristics including low redox potential, high electron transfer
ability, high coordination ability to heteroatoms and used as catalyst for various organic synthesis.
On the other hand, Coumarin derivatives have received considerable attention because of numerous
biological and pharmacological activities such as anticoagulant, and spasmolytic properties. Some
coumarin derivatives, in particular, biscoumarin derivatives are known for their antifungal, anti-HIV,
anti cancer, antimicrobial and the antioxidant activities, urease inhibitory cytotoxicity and enzyme
inhibitory. Also, they have dyeing, optical and fluorescence emission properties. In this present
work, RuCl3. xH2O was investigated as a homogeneous catalyst for a two-component one-pot
condensation reaction between 4-hydroxy coumarin and a range of aromatic, heteroaromatic and
aliphatic aldehydes in water as a solvent (scheme 1). The products were characterized by
spectroscopic methods. (IR, NMR). In conclusion, the chief benefits of this approach include simple,
mild, and green experimental procedure, also moderately broad scope for synthesis of biscoumarins
with high yields (70-95%) and short reaction time (25-35min).
Keywords: Ruthenium, Biscoumarin, Aldehydes, 4-Hydroxycoumarin, Green chemistry
IICC12
179
P-293
Consideration of catalytic effect of Ru compounds on homogeneous synthesis of
flavanone
H. Heidari, K. Tabatabaeian*, M. Mamaghani, N. Mahmoodi
Flavanoid classes of molecules are one of the important area of organic compounds due to excellent
biological profiles reported in the recent times. This class of new chemical entities shows activity in
cancer, AIDS, bacterial and inflammatory diseases. In enzymology, a chalcone isomerase is an
enzyme that catalyzes this chemical reaction. Hence, this enzyme has one substrate, chalcone, and
one product, flavanone. This enzyme participates in flavonoid biosynthesis. In our ongoing studies
of the ruthenium-catalyzed intermolecular coupling reaction between acetophenone derivatives and
a range of alkenes, we decided to consider intramolecular coupling reaction in chalcone derivatives.
In the present work, chalcone was treated with 1,1 diphenylethylene in a molar ratio of 1:5 and Ru
catalysis (6 mol%) in toluene. The reaction mixture was refluxed under an argon atmosphere.The
reaction time for the appearance of product and exhaustion of chalcone was monitored by TLC.
After 1 h, the reaction mixture was purified by preparative TLC, providing the product. The
structure of product was confirmed by IR, 1H NMR and 13C NMR spectra. Results shows that the
main product was flavanone that produced in isomerization as dominant procedure in good yield.
Keywords: Ruthenium, Chalcone, Flavanone
P-294
Synthesis and characterization of new nitrate-bridged polymeric complexesof transition
metal (Hg, Cd and Zn) with phosphorus ylides
F. Hejazi*, S. J. Sabounchei and k. Sanaie-Noorani
Faculty of Chemistry, University of Bu–Ali Sina, Hamedan, Iran
The utility of metalated phosphorus ylides in synthetic chemistry has been well documented. Ylides
containing a second functional group have become increasingly interesting since they can provide
new synthetic and catalytic routes in organometallic chemistry. Recently, sabounchei reported the
first examples of polymeric Hg(II) phosphorus ylide complexes wherein the nitrate anions are
bridging, confirming the general belief that the seven-coordinated complexes would be formed. As
far as we are aware, no Cd(II) and Zn(II) nitrate seven-coordination complexes with this ylide have
been reported to date. In this work we study reactions of ylides Ph3PCHCOC6H4CH3 (Y1),
Ph3PCHCOC6H4OCH3 (Y2) and Ph3PCHCOC6H4NO2 (Y3) with M(NO3)2 · nH2O (M = Hg(II), n = 1,
Cd(II), n = 4 and Zn(II), n = 6) in equimolar ratios using methanol as solvent. The analytical data,
IR, 1H, 13C and 31P NMR indicate a 1:1 stoichiometry between the ylide and M(II) nitrate in each of
complexes of the types [M (Y)(NO3) (µ-NO3)] n.(DMSO)n [M= Hg, Y= Y1 (1), Y2 (2), M= Cd, Y= Y1
(3), Y3 (4) and M= Zn, Y= Y1 (5)]. 31P NMR study for complex 1 indicates disappearance of satellites
with increasing temperature or decreasing concentration. The aims of our present work are to
describe the preparation, spectroscopic characterization of complexes 1, 2, 3, 4 and 5.
Keywords: Polymeric complexs, Phosphorus ylide, Bridging nitrate, Seven-coordinate.
180
IICC12
P-295
Synthesis and spectroscopic characterization of new mononuclear Ag(I) complexes of
some phosphorus ylides
The organometallic chemistry of phosphorous ylides R3P = C (R') (R") (R, R', R"= alkyl or aryl
groups) has undergone a great growth in the last few years, mainly due to their interesting
application as reactants in organometallic and metal-mediated organic synthesis. Juxtaposition of
the keto group and carbanion in the phosphorus ylides allows for the resonance delocalization of
the ylidic electron density providing additional stabilization to the ylide species. The α-ketostabilized phosphorous ylides R3P = C(R')COR" show interesting properties such as high stability
(which allows them to be easily handled in air) and ambidentate character as ligands (C-versus Ocoordination). Reaction of phosphorus ylides of the type Ph3PCHCOC6H4CH3 (Y1), Ph3PCHCOC6H4NO2
(Y2) and Ph3PCHCOC6H4Cl (Y3) with AgNO3 in 1:2 molar ratios using dichloromethane as solvent
yielded mononuclear complexes of the type [(Y)2.Ag]NO3 (Y = Y1 (1), Y2 (2) and Y3 (3)) (Scheme 1).
These compounds were identifie by IR, 1H, 31P, and 13C NMR spectroscopy and elemental analysis.
IR absorption bands observe for C=O stretching in these complexes indicate coordination of the
ylide through carbon. The present study describes the synthesis and characterization of some
mononuclear Ag(I) complexes of phosphorus ylides.
Keywords: Mononuclear complexes, Dichloromethane, Silver (I) nitrate, Phosphorus ylide.
P-296
Synthesis and Multinuclear NMR Study of Novel Complexes of Zn(II) and Cd(II)
Containing Phosphorus Ylides
The coordination chemistry of the phosphoranes of the type R3P+_ C–H2 is well known. Resonance
stabilized phosphorus ylides, particularly the keto ylides are also successfully used as ligands in
organometallic and coordination chemistry owing to their accessibility and stability towards air and
moisture. Although many bonding modes are possible for the ylides. Phosphorus ylides are reactive
compounds, which take part in many reactions of value in the synthesis of organic products. They
are synthetic targets of interest, because of their value for a variety of industrial, biological and
chemical synthetic uses. In this work, we describe the preparation, spectroscopic characterization
(IR and NMR) of complexes of Zn (II) and Cd(II) with ylides Ph3PCHCOC6H4CH3 (Y1) and
Ph3PCHCOC6H4NO2 (Y2) (Scheme 1). The reactions of ylides with ZnCl2 and CdCl2 in equimolar ratios
using methanol as solvent yielded novel binuclear complexes of the type [(R-COCH=PPh3).MCl2]2
(R= CH3, M=Zn (1), M=Cd(2) and R= NO2, M=Zn(3), M=Cd(4)). The characterization of these
compounds was carried out by IR, 1H, 31P, and 13C NMR spectroscopy and elemental analysis. On
the basis of the spectroscopic data we propose that the ligands herein exhibit C-coordination to the
metal centres.
Keywords: Binuclear complexes, Phosphorus ylide, C-coordination, Methanol.
IICC12
181
P-297
Synthesis and characterization of chromium (III) complex of Novel Tetradentate N2O2
–Type Schiff Base Ligand Derived of Acetylacetone and 1,4-Phenylenediamine
R. R. Khojasteh*, S. Hemmati, G. Karimi Nik
Schiff bases have attracted much researcher attention in view of their ability to coordinate metal
ions, acting as multidentate ligands in metal chelates. So, shiff bases have been widely used as
ligands because of high stability of the coordination compounds and their good solubility in common
solvents. The novel ligand 4-[4’-(3-Hydroxy-1-ethyl-but-2-enylideneamino)-phenyl-4-ylimino]-pent2-en-ol (C32H40O6N4Cr2) and the complex of Cr(III) has been synthesized and we have reported
results for the stracture study of the products which examined by 1H,13C NMR, IR, Spectroscopy
and Elemental analysis.
Keywords : Tetradentate Schiff base, 1,4-Phenylenediamine, Acetylacetone, Chromium(III)
P-298
Synthesis of perovskite nanocomposites based on PbZrO3 and investigation of its
physicochemical properties before and after oxidizing agent doping
M. Heydaria, R. Fazaeli*, M. Yousefia
Department of Chemistry, Islamic Azad University, Shahre-rey Branch, Tehran, Iran
Department of Chemistry, Islamic Azad University, south Tehran Branch, Tehran, Iran
a
*
Lead Zirconate (PbZrO3)(PZ) nano-powder with a Perovskite structure and PZ/TiO2 composite
photocatalyst were prepared by sol-gel method. These composites were characterized by powder Xray diffraction, scanning electron microscopy, and transmission electron microscopy. The average
crystallite diameter of the PZ powder is calculated to be ٤٨ nm. Anatase type of titanium dioxide
(TiO2) powder was used in process. The photocatalysed degradation of Acid Yellow 199 and Direct
Red 264 were investigated in aqueous suspensions of PZ/TiO2 under a variety of conditions. The
degradation was studied by monitoring the change in substrate concentration employing UV
spectroscopic analysis technique. The influence of various parameters such as, pH, catalysts,
substrate concentrations, and in the presence of hydrogen peroxide (H2O2) besides molecular
oxygen has been investigated. The degradation product of above mentioned dyes were analyzed by
GC-MS technique. Also, the pores of catalysts were evaluated by BJH technique.
Keywords: PZ/TiO2; Nano-powder; Photocatalysis; Acid Yellow 199; GC-MS; BJH
182
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P-299
Synthesis,characterization,electrochemical and spectroscopic investigation of Ferric
(III) salen Schiff base complex with axial azide ligand
E.Hobbollahi1*,B.Shaabani2
Department of Chemistry. Islamic Azad University Ardabil Branch,Ardabil,Iran
2
Faculty of Chemistry, University of Tabriz,Tabriz,Iran
*
1
Ferric (III) complex with potentially tetradentate salen (H2salen=N,N˝-bis(salicylidene)-1,2phenylendiamine)as equatorial ligand and with axial azid ligand were synthesized and characterized
by IR, UV/VIS, elemental analysis.Electronic spectra and electrochemical properties of the complex
were studied in DMF solutions. Electron spectrum can decrease or increase the intensity of
transmission according to the extent of ligand electropositivity to the central metal, moreover, the
wavelength of absorption band will move about toward the red areas. In the corresponding salen
complex ,the Fe(III)/Fe(II) redox couples are more and Fe(II)/Fe(I) redox couples are less affected
by the characteristics of the axial azide ligand.However,in the case of the salen complex, the
Fe(III)/Fe(II) redox couples have a quasireversible and the Fe(II)/ Fe(I) redox couples have a
reversible characteristics for all kinds of axial azide ligands.
Keywords:ligand,spectroscopy, salen
P-300
Cation-π Interactions: A theoretical study on interaction of hydrated sodium and
magnesium metal ions with fullerene, coronene and benzene
Samaneh Hokmi,a Mahdi Rezaei Sameti,a , Fereshteh Yaghoobi,b Mehdi Bayatb, Sadegh
Salehzadeh*,b
a
b
2Faculty of Chemistry, Bu-Ali-Sina University, Hamedan, Iran
The ability of the π electron cloud of aromatic rings to act as a Lewis base was first systematically
investigated by Tamres in 1951. Recently Pack and his co-workers showed that there is a strong
binding between the hydrogens of magnesium-hexahydrate with π-electron system of aromatic ring
of cytosine. Herein for first time we want to report the interaction energy between the magnesium
hexahydrate as well as sodium hexahydrate with π-electron system of Fullerene. We also compare
the latter interaction with that in simple aromatic compounds such as coronene and benzene. All
calculations were performed at DFT (B3LYP) level of theory using 6-31G** basis set. The
interaction energies were calculated and corrected using basis set super-position error (BSSE) at
same level of theory. The result showed that there is the strong bonding interaction between the
hydrogen atoms of three coordinated water molecules in both magnesium and sodium hexahydrate
with π-electron system in fullerene (Fig 1.). Also the result showed that the interaction energy
between the magnesium hexahydrate with all π-electron systems studied here is more than that for
sodium hexahydrate.
Keywords: Cation-π Interactions, Density Functional Theory study, Fullerene.
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P-301
Synthesis and characterization some new lead(II) Coordination polymers with nitrogen
donor ligands:
Marzieh Hooshyara , Mohammad Jaafar Soltanian Farda* , Ali Morsalib
Department of Chemistry, Islamic Azad University, Firoozabad branch.P.O. Box 74715-117,
Firoozabad,Fars, Iran
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155-4838,
Tehran, Iran
([email protected])
a
b
Some new Lead(II) coordination polymers with nitrogen donor ligands such as 3,5 bis(2-pyridyl),4amino,1,2,4-tri azol(2-abpt) and 3,5 bis(4-pyridyl),4-amino,1,2,4-tri azol(4-abpt)
has been
synthesized using branched tube and reflux method and characterized by CHN elemental analysis,
IR, 1H NMR,UV-Vis spectroscopy and studied by thermal as well as X-ray crystallography,
respectively. The thermal stability of compound was studied by thermal gravimetric analysis (TGA)
and differential thermal analysis (DTA) diagrams too.
Keywords: lead(II) , Nitrogen donor ligand, Coordination polymers,
P-302
Synthesis and characterization of Platinum(II) complex with tetradentate Schiff Base
containing S2N2 donor atoms
M. Hoseinia, B. Shafaatiana,* , A.R. Hasaninejadb
b
Department of Chemistry, Persian Golf Univesity , Bushehr, Iran
a
Schiff bases are considered as a very important class of organic compounds which have wide
applications in many biological aspects. These wide applications of Schiff bases have generated a
great deal of interest in metal complexes. Schiff base–transition metal complexes are one of the
most adaptable and thoroughly studied systems. These complexes have also applications in clinical
and analytical fields. Some of Schiff base complexes are used as model molecules for biological
oxygen carrier systems. Tetradentate Schiff base complexes are well known to form stable
complexes, where the coordination takes place through the N2O2 donor set. The coordination
chemistry of platinum (II) has attracted a considerable attention due to its biological applications
and tumor treatment based on the early discovery of antitumor activity of cis-platin. In this study,
platinum metal was converted to platinum salts such as K2PtCl6 and K2PtCl4 and a new tetradentate
Schiff base with S2N2 donor atoms was reacted with K2PtCl4 at 45 °C in methanol and formed 1:1
(Pt(II):Schiff base) stoichiometry with square planar geometry. Different conditions such as
temperature, reaction solvent and time of reaction was investigated. The platinum Schiff base
complex was characterized by IR spectroscopy, 1HNMR and elemental analysis.
Keywords: Platinum complex, Schiff base, Elemental analysis, Platinum(II)
184
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P-303
New bisamide Ligands Containing N,N- bis (2-quinoline carboxamide)ethylenediamine
and Their Complexes: Synthesis and Characterization
N. Hosseini, A. Zamanpour*
Quinolines have because for the preparation of nano and mesostructures with enhanced electronic
and
photonic
properties.A
new
tetradentate
ligand,
N,N-bis(2Quinolinecarboxamide)ethylenediamine synthesized from 2 molar Quinaldicacid and one molar
ethylenediamine. The solid complexes of copper(II) and nickel(II) with the neutral and the
deporotonated ligands have been synthesized and characterized by NMR, IR, UV-Vis and ESR
Spectroscopy. The thermodynamic and structural properties of these complexes show the ionization
of amido nitrogen atom when it is coordinated to the metal center. The complexes obtained with
the deprotenated forms of the ligands imply the coordination through the Nitrogen atoms of the
amidic groups. Identity of such a reaction product was confirmed by microanalytical and IR spectral
data. The spectral properties of this ligand exist of a sharp pick in limited 3000 that related to amid
amidio groups and destroy it when the metals bind to the ligand.
Keyword: Macrocycles, Quinoline, Quinaldic acid, Amido group, Deprotenated.
P-304
Investigation on Thermal Analysis of pyrotechnic Reactions Containing Silicon Powder
as Reducing Agent and Some Inorganic Oxidizing Agents
S. G. Hosseini, A. Eslami*
Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar, Iran
(e-mail: [email protected] )
Pyrotechnic compositions are typically composed of finely divided mixtures of metallic or nonmetallic elements as reducing agent with inorganic oxidizing agents and which are used to
chemically generate heat, light, or color for smoke dye, emergency signaling, fireworks, air bag
inflators, and special effects devices of the entertainment industry. Thermal techniques containing
differential thermal analysis and thermogravimetry provide powerful methods for these following
reactions in solid state pyrotechnic compositions. In this study, solid state reaction of several binary
pyrotechnic systems using metallic silicon powder as reducing agent and one of the following
oxidants: KMnO4, KNO3, KClO4, Ba(NO3)2, PbO2, Pb3O4, Na2Cr2O7, NH4NO3 and KClO3, were
investigated. Differential thermal analysis and thermogravimetry techniques have been employed to
elucidate the reaction mechanism of these pyrotechnic systems in solid state. Among investigated
mixtures only pyrotechnic systems containing KMnO4, Na2Cr2O7 and NH4NO3 were not ignited during
thermal analysis, and do not have suitable pyrotechnic properties. Based on thermal analysis and
reaction temperatures of these pyrotechnic mixtures, relative reactivity of these mixtures was found
to obey in following order:
Si+KClO3> Si+PbO2 > Si +KClO4> Si +Ba(NO3)2 > Si +Pb3O4 > Si +KNO3
This trend can be considered as essential experimental data to interpretation of investigated
mixtures in pyrotechnic industry.
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185
P-305
Uncommon Rate Enhancement in Oxidative Addition Reaction of Allyl Bromide with
Organoplatinum(II) Complex [Pt(CH3)2(bpy)]: A Comparative Kinetic Study
a
S. J. Hoseinia,*, M. Rashidib
[email protected]
b
Department of Chemistry, Faculty of Sciences, Shiraz University, Shiraz, 71454, Iran
Oxidative addition reaction is a fundamental step in many synthetic and catalytic organic reactions,
especially carbon-carbon coupling reactions. The allyl bromide was oxidatively added to the
[Pt(CH3)2(bpy)] complex , in which NN = bpy (2,2′-bipyridyl), to give the platinum(IV) complex
[Pt(CH3)2(C3H5)(Br)(NN)]. Kinetics of the reactions in benzene and acetone were studied using
UV/Vis spectrophotometery and a common SN2 mechanism was suggested .The second-order rate
constants were approximately 1500-2000 larger than those involving the corresponding reaction
with n-bromo propane. The process is under investigation, however it is proposed that the ratedetermining step involves the formation of a η3-allyl complex [Pt(η3-CH2CHCH2)(CH3)2(bpy)]Br that
eventually collapses to give the final product [Pt(CH2CHCH2)(Br)(CH3)2(bpy)]. The reactions
proceeded almost exclusively with a trans addition although based on the NMR spectrum, a trace of
the cis isomer was also tentatively assigned.
P-306
Pentacoordinated Zinc (II) complex; Synthesis, Characterization, Thermal and
Fluorescence properties
a
A. Hosseiniana,M. Movahedib, A. R. Mahjoubc
Tehran, Iran
b
Department of Chemistry, Payame Noor University, Isfahan, Iran.
c
Department of chemistry, Tarbiat Modares University, Tehran, Iran
In coordination chemistry many studies are on the interaction of Zn2+ ion with biomolecules.
Pentacoordinated complexes of Zn(II) are known but are relatively rare. In this paper, we represent
one new complex with a pentacoordinated environment of Zn(II) in a trigonal – bipyramidal
geometry. The pentacoordinated geometry suggests that this coordination is energetically favored
and may be important in biological systems. The reaction of Zn(NO3)2.4H2O with 2,2'-diamino-5,5'dimethyl-4,4'-bithiazole Ligand leads to [Zn(DADMBTZ)3] (NO3)2.CH3OH complex. The
characterization was done by IR, 1H, 13C NMR spectroscopy and single crystal X-ray determination.
In complex, one of DADMBTZ ligands acts as a monodentate ligand to form the five coordinated
Zn(II) complex, giving distorted trigonal bipyramidal geometry around the metal. The UV-Vis
spectra of compound display intense absorption bands at 275 nm, have been ascribed to the
bithiazole π -π* and n- π* transitions. The luminescence spectra of the compound exhibit an
emission at 363.2 nm assigned to the bithiazole interligand transitions. No emission originating from
metal-centered and MLCT or LMCT excited states are expected for the Zn(II) complex, since the
Zn(II) ion is difficult to oxidize or reduce due to its d10 configuration. The thermal behavior of
compound was studied by thermal gravimetric and differential thermal analyses.
Keywords: Pentacoordinated, Bithiazole; Zinc(II) complex; Thermal, Luminescence
186
IICC12
P-307
Synthesis and study on coordination properties of the bidentate axial ligands to bridge
Co(salen) to [60]fullerene
Nasim Hossein Abadi and Bahram Ghanbari*
[email protected]
The ability of fullerene C60 as an acceptor to form charge transfer complex with a variety of donor
molecules such as calixarenes, crown ethers, phenols and amines is a subject of extensive ongoing
interest. Furthermore, cobalt(II)di-(salicylal)-ethylenediimine (Co(salen)) complexes are the
catalysts that has been extensively used in oxidation of phenols, amines and recently as the
catalysts for C60 oxidation by our group. Basically, in the course of the oxygen uptake, Co (salen)
preferentially needs the axial base to follow its catalytic functions. The aim of this study at the
outset is synthesis of bidentate ligands having the ability to interact simultaneously with C60 and Co
(salen). Hence, four Schiff base ligands with pyridinic electron donor moiety in one side, and such
electron donor moiety as pyridine, phenol and aniline in another side were synthesized. In the next
step the interaction of these Schiff base ligands with Co (salen) and C60 in the mixture of two
solvents, i.e. toluene/dimethylsulfoxide was explored separately by UV-visible spectroscopy while
their kinetic studies were also undertaken. On the other hand, the triplex interactions of Co (salen),
C60 and each of the ligands in the same solvents were investigated. The remarkable changes in
triplex mixtures confirmed the behavior of the ligands as the bridging group between Co (salen)
and C60. According to the obtained rate constants, the rate of triplex interactions for different Schiff
bases showed remarkable differences.
Keywords: Schiff base, Co(salen), C60, Interaction
P-308
Synthesis, Characterization, and Solution Studies of Cobalt(II) Complexes of Schiff
Base Ligands
S. A. Hosseini-Yazdi*, A. A. Khandar, F. Zolfi
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666-14766,
Iran
Expansion of our fundamental understanding of the cyclization processes allows diversity of ligands
to be synthesized as artificial cationic, anionic, and neutral guest receptors. Introduction of a
template agent is the most reliable method to prevent oligocondensation. Use of metal ions with
different ionic radii and coordination requirements makes it possible to control the structure of the
product formed. We report here synthesis and spectral and electrochemical properties of cobalt
complexes. The cobalt (II) complexes of three Schiff base ligands were synthesized by Schiff base
condensation of 2-[3-(2-Formylphenoxy)-2-hydroxypropoxy] benzaldehyde (PL) with 1,2diaminopropane and 1,2-diaminoethane, and diethylenetriamine in the presence of cobalt (II) salts.
The isolation of complexes of cobalt (II) has been carried out and conductance measurements, IR,
UV-Vis absorption, and electrochemistry have been employed to probe the nature of the respective
complexes in both solid and solution states. The infrared spectrum of dialdehyde PL shows a
carbonyl mode at 1679 cm-1. The condensation of PL in the presence of Co (II) results in isolation
of the corresponding complexes of the Schiff base ligands. Conversion of the aldehyde groups into
Schiff base derivatives is confirmed by the absence of carbonyl absorption (1679 cm–1) bands and
appearance of strong bands between 1643-1650 cm–1 assignable to the ν(C=N)imine groups.
Keywords: Schiff Base; Cobalt; Template; Electrochemistry
IICC12
187
P-309
Copper(II) Complexes of a 30-Membered Aza-Crown Macrocycle: Synthesis,
Characterization, X-ray Structures and Solution Studies
S. A. Hosseini-Yazdi*, A. A. Khandar, H. Kalantari
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666-14766,
Iran
There is a continuing interest in the chemistry of aza and oxa-aza macrocycles containing different
pendant arms because of their ability to act as selective complexing agents for metal cations. The
30-membered mixed-donor macrocycle L, which contains N4O10 donor set, was synthesized. Also
three copper(II) complexes of L have been synthesized and characterized by X-ray crystallography,
FT-IR, UV-Vis absorption spectroscopy, elemental analysis and electrochemistry. The structure of
complexes shows an unexpected anion dependence. Reaction of copper(II) acetate with L afforded
a dinuclear complex. When L reacts with copper in presence chloride and nitrate anions the product
is a novel coordination polymer. Contrasting with these, when SCN− is used, the product complex is
a mononuclear complex. The X-ray determination indicate that the complexes contain copper(II) in
square pyramidal ligand field. Also a geometrical analysis has been performed on π−π stacking and
weak hydrogen bonds in metal complexes.
Keywords: Copper; Macrocyclic Ligands; Anion-Dependent Structure; Alcohol Pendant Arm
P-310
Synthesis and multinuclear NMR study of new orthopalladated, mononuclear and
dinuclear Pd(II) complexes of some phosphorus ylides
a
S. J. Sabouncheia, M. HosseinZadeha,*, F. Akhlaghia and V. Jodaianb
Faculty of Chemistry, University of Bu–Ali Sina, Hamedan, 65174, Iran
b
University of Islamic Azad, Islamshahr Branch, 33135/369, Iran
The utility of metalated Phosphorus ylides in synthetic chemistry has been well documented.
Phosphorus ylides are remarkable ligands which have attracted much attention in synthetic,
catalytic and theoretical fields of transition metal chemistry. Ylides containing a second functional
group have become increasingly interesting since they can provide new synthetic and catalytic
routes in organometallic chemistry. The aims of our present work are to describe the preparation,
spectroscopic characterization of complexes 1, 2 and 3. Reaction of PdCl2 with{Ph3PCHCOC10H7}(Y1)
in a 1:2 ratio in acetonitrile at room temperature results the complex [Ph3PCHCOC10H7]2PdCl2 (1)
along with the phosphonium salt [Ph3PCH2COC10H7]Cl. The same reaction in a 1:2 molar ratio with
{Ph3PCHCOCH2COOC2H5}(Y2) at the reflux temperature gives a dinuclear complex of
[Pd{CHP(C6H4)Ph2COCH2COOC2H5}(µ-Cl)]2
(2)
along
with
the
phosphonium
salt
[Ph3PCH2COCH2COOC2H5]Cl. This complex reacts with PPh3 in a 1:2 molar ratio in dichloromethane
to give the product of bridge-splitting [Pd{CH{P(C6H4) Ph2}COCH2COOC2H5}Cl(PPh3)] (3). The
characterization of these compounds was carried out by IR, 1H, 31P and 13C NMR spectroscopy and
elemental analysis.
Keywords:. Phosphorus ylide, Orthopalladated, Triphenylphosphine.
188
IICC12
P-311
Synthesis, characterization and crystal structure determination of two Hg(II) dimer
complexes: [{Ph3PCHCOCH2COOC2H5}·HgBr2]2 and [{Ph3PCHCOCH2COOC2H5}·HgI2]2
M. HosseinZadeh*, S. J. Sabounchei, A. Dadras** and F. Akhlaghi
*Faculty of Chemistry, University of Bu–Ali Sina, Hamedan, 65174, Iran
**Department of chemistry, University of Urmia, Urmia, 57165, Iran
The reaction of the ylide {Ph3PCHCOCH2COOC2H5} (EAPPY) with mercury(II) bromide and
mercury(II) iodide in equimolar ratios using methanol as the solvent produces crystals of
[(EAPPY)·HgBr2]2 (1) and [(EAPPY)·HgI2]2 (2), respectively. Both complexes were thoroughly
characterized by elemental analysis, IR, 1H, 31P and 13C NMR spectroscopy and single-crystal X-ray
diffraction methods. Single-crystal X-ray analysis reveal the presence of centrosymmetric dimeric
structures containing the ylide and HgX2 (X= Br or I) in both cases. 1 and 2 crystallize in the space
group PC of the monoclinic and P-1 of the triclinic systems and contain 2 and 1 molecules per unit
cell, respectively.The unit cell dimensions for 1 are: a= 10.4551(9) Ǻ, b= 11.8372(9) Ǻ, c=
20.9539(17) Ǻ and α= 90˚, β= 98.658(7)˚, γ= 90˚ and for 2 are: a= 10.2208(7) Ǻ, b= 10.8141(7)
Ǻ, c= 12.9264(8) Ǻ and α= 72.206(5)˚, β= 72.207(5)˚, γ= 73.452(5)˚. The Hg(II) center forms
four close contacts with sp3 hybridization and has a 4-coordinate environment with one short Hg-X
bond, one Hg-C bond and two asymmetric bridging Hg-X bonds at distances of 2.779(2) and
2.831(2) Ǻ in 1 and 2.603(3) and 3.022(2) Ǻ in 2.
Keywords: X-ray crystal
Triphenylphosphine.
structure,
mercury(II)
dimmer
complexes,
Phosphorus
ylide,
P-312
Synthesis of 1, 4- Dihydropyridines derivatives by using RuCl3.nH2O as a homogeneous
catalyst
S. Houshyar, K. Tabatabaeian*, M. Mamaghani
*
Ruthenium stands extensively among other platinum group metals in terms of its coordination and
organometallic chemistry.Electron transfer reactions are fundamental and play an important role in
chemical and biological processes. Ruthenium (III) chloride can be used as a mild and efficient
catalyst in many reactions. 1,4-Dihydropyridines (1,4-DHPs) are important class of compounds in
the field of drugs and pharmaceuticals. The heterocyclic ring in DHP is a common feature of various
bioactive compounds such as antidiabatic, antianxiety, antidepressive, antitumor, and
antiinflammatory agents. DHPs are commercially used as calcium channel blockers for the
treatment of cardiovascular diseases. According to the properties of Ru mentiond earlier, we
decided to synthesis 1,4-Dihydropyridines utilizing RuCl3.nH2O as catalyst. A mixture of dimedone,
aryl aldehydes, NH4OAc and RuCl3.nH2O in EtOH was refluxed for the required reaction time. The
desired products were identified by melting point, IR and 1H-NMR spectra. In conclusion, we report
a simple protocol for the synthesis of fused 1,4-dihydropyridines using RuCl3.nH2O as an efficient
catalyst. The desired compounds were synthesized in high yields(70-98%) and shorter reaction time
(1-3.5h).
Keywords: 1, 4-Dihydropyridine, Dimedone, Aldehyde, RuCl3.nH2O.
IICC12
189
P-313
Synthesis, spectroscopic characterization and X-ray crystallography of mixed-metal
polymeric complex; [WS4Ag2(Imt)2]n with AgS5 square-based pyramid site (Imt =
imidazolidine-2-thione)
a
R. Hyvadia , A.Beheshtib*
Department of Chemistry, Shahid Chamran technical and vocational institute, Ahvaz, Iran.
([email protected])
b
Department of Chemistry, Faculty of Sciences, Shahid Chamran University, Ahvaz, Iran.
([email protected])
The interaction of heterocyclic thiones with transition metals has attracted much attention, due to
the biochemical significance and their use as medicinal substances. Reaction of AgI with salt of
[WS4]2− with imidazolidine-2-thione (Imt) give the complex [WS4Ag2 (Imt) 2]n. The title complex has
a rather complicated polymeric structure in which the structural repeat unit contains two
inequivalent tetrahedral WS42− units, four Ag atoms in three different environments, and four Imt
ligands coordinated only to Ag through their S atoms and engaging in a range of N–H· · · S
hydrogen bonds to both tetrathiometallate and Imt S atoms. Imt ligands are terminally coordinated
to Ag. Ag (3) has a coordination number of 5, and is the first example of a five coordinate AgS5
unit. The structure also have been characterised by infrared, UV-Vis and 1H and 13C NMR
spectroscopy.
Keywords: Heterocyclic thione, Ag complexes; tetrathiometallate, mixed-metal
P-314
The first complex of hexasulfido zinc (II) with tetrathiometalates
a
([email protected])
b
([email protected])
Mixed-metal complexes in which one or more MLn units are attached to [M'S4]2− are very common
(M = Zn and M' = W). In the [(PPh4)2[Zn (WS4) 2] complex two WS4 are coordinated to a central
Zn2+.The title complex, (Ph4P)2[(S)2W(µ-S)2Zn(S6)]·(CH3)2O, both metal centers have distorted
tetrahedral coordination, the two tetrahedral sharing an S···S edge. In W, the minor distortion
consists mainly of an elongation of the bonds to the bridging S atoms relative to the terminal S
atoms. Both distance and angle distortions are found for Zn: the bonds to the bridging sulfido
ligands are significantly longer than those to the chelating hexasulfido ligand, and the angle
between the bridging ligands is markedly reduced from the ideal tetrahedral value. The central
four-membered WS2Zn ring is approximately planar. The S62− ligand, together with the Zn centre,
has a crown-like conformation [4], with torsion angles around the S—S bonds slightly exceeding the
range 80–100 Å with alternating positive and negative signs.
Keywords: hexasulfido ion, Zn complexes; tetrathiometallate, mixed-metal
190
IICC12
P-315
Synthesis, spectroscopic characterization and X-ray crystallography of (TpMe, Me) Zn
(OAc) complex as a model of the active site of the carbonic anhydrase enzyme [TpMe, Me
= hydrotris (3,5-dimethylpyrazolyl) borate and OAc = acetate]
a
([email protected])
b
( [email protected])
Numerous studies have been performed to synthesize stable tetrahedral metal complexes MX
(TpR,R’) (M = Zn, Cd, Cu; X = Cl, OAc) by use of sterically tridentate nitrogen donor ligands to
model the structure of the active site of the carbonic anhydrase enzyme.The title complex contains
a tripodal pyrazolyl borate [3], a monodentate acetate and a ZnII centre in a distorted tetrahedral
coordination environment capped on one triangular face by a secondary Zn---O interaction with the
second O atom of the acetate ligand. The four-coordination of ZnII and the essentially monodentate
character of the acetate ligand are due to the high steric demands of the ligand set, which prevent
chelate formation and five-coordination and lead to relatively long Zn—O and Zn—N bonds
compared with related complexes of ZnII and other metals.
Keywords: carbonic anhydrase, Zn complexes, tetrahedral coordination, monodentate acetate
P-316
Chain polymer of silver (I) with bulky heterocyclic thione ligand, Diap (Diap = [1, 3]
diazepane-2-thione)
a
R. Hyvadia, A.Beheshtib*
([email protected])
b
([email protected])
The chemical interest of thione ligands lies in the fact that they are potentially ambidentate or
multi-functional donors with the exocyclic S and heterocyclic N atoms available for coordination, and
their biological interest arise from their structural analogy to thiolated nucleosides. The chain
polymer complex; C5H10AgIN2S has a simple empirical formula but a rather complex solid-state
structure. The unit contains three AgI atoms, three I atoms, and three Diap ligands. All three Diap
ligands act as bridges between pairs of Ag atoms. The three independent Ag atoms are all fourcoordinate. The principal distortion is the small angle in the Ag2I2 ring, has large distortions
associated with the formation of a direct Ag–Ag bond of length 2.9800Å and slightly longer than the
shortest distance in silver metal (2.886A˚). N–H· · · I hydrogen bonds involve all six NH groups and
all three I atoms; they occur exclusively within polymeric chains and not between them.
Keywords: Heterocyclic thione, Ag complexes; chain polymer, hydrogen bond
IICC12
191
P-317
Hierarchical Nanostructure of Cadmium Oxide Synthesized by Mechanochemical Method
M. Imani, A. Tadjarodi*
Cadmium oxide (CdO) is a n-type semiconductor with a direct band gap of 2.5 eV and an indirect
band gap of 1.98 eV, that creates optical, optoelectronic, sensing and catalytic properties. It was
used for different applications such as solar cells, photo transistors, transparent electrodes,
catalysts and gas sensors. Various techniques are reported so far to synthesize CdO in different
morphologies such as solvothermal/hydrothermal, sonochemical, templating methods, and chemical
vapor deposition (CVD), high-energy ball milling and annealing process and so on. Nowadays
considerable attention has paid to mechanochemical procedure, because of mechanical milling is an
effective, useful, low cost and simple processing technique extensively used to the preparation of
different structures. In this study, Cadmium oxide nanostructure (CdO) was prepared via a
mechanochemical reaction of Cd (NO3)2.4H2O and CH3CONH2. The result powder (precursor) was
calcined at 450°C for 2 h. The product was characterized by FT-IR, XRD, SEM and TEM. SEM and
TEM images show hierarchical nanostructure like a cauliflower including nanorod, nanotube, cubic
nanoparticles
Keywords: Cadmium oxide, Mechanochemicl reaction, Hierarchical nanostructure, Urea.
P-318
Effect of some biological ligands on serum Iron and tin uptake in rats
M. Iranmanesha, A. Amirib,*
a. Department of chemistry, Islamic Azad University Kerman Branch, Kerman, Iran
b. Department of chemistry, Vali-e-Asr University of Rafsanjan, Rafsanjan, Iran
Corresponding Author Email: Amiri @ vru.ac.ir)
The effects of two known biological ligands deferiprone (1,2-dimethyl-3-hydroxypyrid-4-one, L1) and
desferrioxamine (DFO) might be more efficient as combined treatment than as monotherapies in
removing tin from blood was tested in rats. Six- week- old male wistar rats received chelators. L1
(p.o.), DFO(i.p.) or L1+DFO as 220 mg/kg dose half an hour after a single i.p. administration of 25
mg/kg body weight in the form of chloride. Serum tin concentration and serum iron concentration
were determined by graphite furnace and flame atomic ansorption spectrometry (GF AAS and F
AAS) methods respectively. The chelation therapy results show that DFO and L1 are able to remove
tin ions from blood while iron concentration returned to the normal level [1]. The efficiency of
DFO+L1 is more than DFO or L1 in removing tin from blood. Our results support the usefulness of
this animal model for preliminary in vivo testing of tin chelators in human.
Keywords: Desferrioxamine, Deferiprone, Tin toxicity, Chelation therapy and rats
192
IICC12
P-319
Effect of Exjade, Exjade+DFO and Exjade+L1 ligands on serum Iron and Aluminium
uptake in rats
M. Iranmanesha, S. J. Fatemib,*, A. Shokooh Saljooghib, F. Dahooee baloochb, M. R. Golbafanb
a. Department of chemistry, Islamic Azad University Kerman Branch, Kerman, Iran
b. Department of chemistry, Shahid Bahonar University, Kerman, Iran
Corresponding Author Email: [email protected])
This study investigates the complexation and biological effect of of Exjade, Exjade+DFO and
Exjade+L1 ligands on removing of aluminium ions in rats [1,2]. At first, wistar rats were fed
aluminium chloride at doses of 20 and 40 mg/kg body weight for a month. At the end of this time,
chelation therapy was done by using of Exjade, Exjade+DFO and Exjade+L1 ligands for a week. In
all of the procedures a control group was used that were fed by water and standard food. After a
week, animals were killed by CO2 gas and from blood was sampled. Samples were digested by
HNO3 and the concentration of iron and aluminium were determined by atomic absorption
spectroscopy method. Results were showed that the concentration of aluminium after chelation
therapy was decreased. Toxic symptoms were decreased obviously and iron concentration of blood
was received to normal level. So these chelatores were useful in removing of aluminium element
from body of experimental rats. Also combination of Exjade+DFO and Exjade+L1 ligands are more
effective than exjade individually for removing of aluminium ions.
Keywords: Exjade, Desferrioxamine, Deferiprone, Aluminium toxicity, Chelation therapy and rats
P-320
Theoretical investigation on electronic and structural properties of the trinuclear
mixed- metal complexes of Ag-Hg and Au-Hg
D. Farmanzadeh*, M. Jafary
Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
In recent years, the trinuclear mixed- metal complexes have been attracted considerable interest
and studied extensively both experimentally and theoretically, because of their unusual and unique
electronic and magnetic properties compared to their pure counterparts. Herein we theoretically
investigated, the structural and electronic properties of the trinuclear mixed silver- mercury
[Ag2Hg(HOC=NH)3] and gold- mercury [Au2Hg(HOC=NH)3] compounds. All calculations were
performed with the density functional theory at the B3LYP level by Gaussian 03 program. The
LanL2DZ basis set for the gold, silver and mercury atoms and the 6-31G* basis set for other atoms
are used. The bond angle of Ag-Hg-Ag and Au-Hg-Au is considered 60 degree in these two
complexes. The results show that, in the silver- mercury compound, the Ag-Ag and Ag-Hg bond
lengths are 3.49 and 3.87Å and in the gold- mercury compound, the Au-Au and Au-Hg bond lengths
are 3.54 and 3.74Å respectively. Value of the electric dipole moment of gold- mercury is higher than
those for the silver- mercury complex. The calculated gap between the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), or simply the HOMO-LUMO
gap (HLG) for different spinorbitals shows that the values of HLG(α–α) and HLG(β–β) both for α
and β electrons in gold- mercury complex are higher than those for the silver- mercury complex.
Keywords: Theoretical investigation, Electronic properties, Mixed- metal, B3LYP method,
IICC12
193
P-321
Synthesis and characterization of some new Schiff base compounds from 3,4diaminobenzoic acid and their interactions with the metal ions
T. Jafari , Kh. Mohammadi , M. Niad*
Department of Chemistry, College of Sciences, Persian Gulf University, Bushehr, 75169, I.R. Iran
[email protected]
Schiff bases (Sb) derived from aromatic amines and aromatic aldehydes are widely applicable in
inorganic, biological and analytical chemistry. Schiff base improved conservative reactions such as
allylic alkylation, hydrosilation of acetophenones, decomposition of hydrogen peroxide, Michael
addition, annulation, carbonylation, Heck reaction, benzylation of alanine, amidation and
aziridination of hydrocarbons, isomerization of norbornadiene to quadricyclane, addition of cyanides
to imine, cyclopropanation, silylcyanation of aldehydes, desymmetrization of meso compounds,
Diels–Alder reaction, aldol condensation
reaction. The compounds are synthesized from
condensation of salicylaldehyde derivatives with 3,4-diaminobenzoic acid in methanol solution and
characterized by FT-IR and 1H NMR. All Schiff bases show fluorescence properties that may use in
various purposes. We have been studying the interactions of corresponding Sb with some metal
ions by spectrophotometric method
Keywords: Schiff base, 3,4-Diaminobenzoic acid , Aromatic aldehydes, Fluorescence,
Spectrophotometric
P-322
Synthesis and characterization of six-coordinate mono dioxomolybdenum(VI) complex
containing bidentate naphthalenediamine ligand
R. R. Khojasteh*, M. Jafarzadeh, B. Hazizadeh
Corresponding Author E-mail: [email protected]
The incorporation of ancillary ligands with different donor properties into metal peroxides gives
complexes which exhibit intriguing lability differences. The chemistry of the peroxo complexes has
received considerable attention in recent years, mainly because they are sources of active oxygen
atoms and can be used as stoichiometric, as well as catalytic oxidants for organic and inorganic
substrates. Reaction of peroxo molybdenum (VI) with naphthalenediamine has been done. In this
research first of all we prepared peroxo molybdenum (VI) and methanolic solutions of the peroxo
complex were titrated with Ce(IV) to determine the number of active oxygen atoms present, then
mixed it with naphthalenediamine and we studied different aspects of this synthesis. The structure
of the product was examined by 1H, 13C_NMR, IR spectroscopy and elemental analysis.
Keywords: dioxomolybdenum(VI); naphthalenediamine; peroxomolybdenum(VI)
194
IICC12
P-323
Crystal Structure of Tricarbonylrhenium(I) bromide complexes
Maryam Jahanbakhshian§, Saeed Dehghanpour*† and Ali mahmoudi§
† Department of Chemistry, Alzahra University, P.O.Box 1993891176, Tehran, Iran
§Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
Study of tricarbonyl rhenium(I) complexes are of great interest under the point of view of various
applications like solar energy conversion, catalytic activity and their usage in the photoreduction
and electroreduction of CO2 to CO. The molecule of the complex is located on the crystallographic
twofold symmetry axis and thus one-half of the molecule is the asymmetric unit of the compound.
At the Re center, the Br ligand and CO group trans to it are mutually disordered by axial twofold
symmetry, with each group being present at each location with site occupancy of 50%. The steric
requirements of the bidentate ligands cause distortion of the octahedral coordination which is most
clearly seen for the ligand bite angles (N(10)–Re(1)–N(10a), 78.4(2) and the trans angles at the
ReI site are in the range 173.7(4)-177.8(10), showing also deviation from an ideal octahedral
arrangement. The coordinated bromide is slightly titled toward the ligand, L1, causing a narrowing
of the N–Re–Br angles (87.29(16)o for N(10)–Re(1)–Br(2)). The Re–N bond lengths are similar and
the distances are within the range expected for such complexes. The rhenium–carbonyl bond
lengths do not show any significant differences [1.914(6) and 1.921(15) Å] but are consistent with
those observed in similar complexes. The Re–Br bond length, 2.5605(17) Å, is similar with the
reported compounds. Despite the fact that the donor N-atoms are sp2-hybridized, the chelate ring is
significantly puckered in this complex, and some strain in the chelate ring is suggested by deviation
from 120o angle about the N-atom.
P-324
Ultrasonic-assisted synthesis of Perovskite-type lanthanum cobalt oxide nanocrystals
a
S. Jahania, M. khorasani-Motlagha,*, M. Noroozifara
Intensive research is devoted to the perovskite type oxides based on rare earth and 3d transition
elements properties with formula LaMeO3 (Me: Mn, Co, Fe). Therefore, a lot of attention was given
recently both on the magnetic and electrical properties and the preparation method of these
materials. Activity and stability of catalysts are strongly related to material properties such as
particle size distribution, morphology and crystallinity that are on their turn controlled by the
method of synthesis. LaCoO3 is an important material, being used as an oxidation and electro
catalyst. LaCoO3 is especially suitable as an air electrode material for high-temperature solid oxide
fuel cells (SOFC) because of its chemical stability at high temperature and its superior
electrocatalytic property. Here, the synthesis of perovskite-type oxides, LaCoO3, using ultrasonic
was investigated by adjusting the composition of the precursor solution and the temperature of
synthesis and calcinations. The nanocrystalline product was characterized by Fourier transform
infrared (FT-IR), x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive xray spectrometer (EDX), and vibrating sample magnetometer (VSM). The results indicated that, the
crystalline phase of LaCoO3 became more precise with increasing calcination temperatures and the
particle size increased with increasing calcination temperatures.
Keywords: Ultrasonic, Perovskite, LaCoO3, XRD, SEM, VSM
IICC12
195
P-325
Co-precipitation preparation of LaCoO3 nanocrystals in the presence of
different surfactants and its characterization
a
S. Jahania, M. khorasani-Motlagha,*, M. Noroozifara
Department of Chemistry, University of Sistan & Baluchestan, Zahedan, Iran
Pervoskite – type complex oxides are of great interest and have been widely studied for their
various properties and applications in the recent decades. These materials have been used quite
effectively for catalytic oxidation reaction including hydrogenation of hydrocarbons, ammonia
oxidation and catalytic combustion. Several synthesis methods for preparation of pervoskite phases
have been proposed and developed, for example pyrolysis, co-precipitation, citrate complexation,
sol-gel process. In present study, preparation of LaCoO3 was achieved by, aqueous solution of
lanthanum and cobalt chloride were prepared and mixed together in 1:1 molar ratio and then was
added small amount of surfactants. For the pH control, NaOH was dropped into the precursors. The
precursor was dried at 100°C for 8h and calcinated at 1100°C for 4h. The results indicated that the
amount of surfactant, pH and rate of stirring were played an important role in the homogeneity and
size of product. It is assumed that when the NaOH solution was added dropwise into the mixture
solution, some small LaCoO3, crystal nuclei was formed at the initial stage of the reaction. With the
increase of the NaOH solution, the slowly produced LaCoO3, crystallites grew on the basis of the
initially formed LaCoO3, crystal nuclei. The nanocrystalline LaCoO3 was characterized by FT-IR, XRD,
SEM, EDX and VSM.
Keywords: LaCoO3, Peroveskite oxide, Co-precipitation, Nanocrystals, Rare earths
P-326
Ecofriendly Epoxidation of Alkenes With Molecular Oxygen Catalyzed by Immobilized
Co(acac)2 and Co(bpy)2Cl2 complexes Within Nanoreactors of Al-MCM-41
M. Jalalian, F. Farzaneh*
Department of Chemistry, University of Alzahra , Vanak, Tehran, Iran
[email protected]
The development of environmentally benign technologes, i.e. the heterogenization homogeneus
catalysts, has been given much attention in catalytic research field. The encapsulation of metal
complexes in porous materials is very attractive because the prepared materials could act as mimic
enzymes. Selective oxidation of organic compounds with simple oxidants such as cheap, abundant,
and nontoxic dioxygen is an example of an attractive approach for high varieties of ecologically
sustainable chemical processes. In this study attempt has been made for encapsulation of cobalt
complexes with different ligands such as bipyridine, and acetylacetonate within nanoreactors of AlMCM-41. The immobilized complexes were characterized by XRD, N2 -adsorption desorption, FT-IR
and UV-VIS techniques. It was also found that Co(bipy)22+/Al-MCM41and Co(acac)2/Al-MCM-41
catalyzed successfully the epoxidation of norbornene, styrene, cis-stilbene, trans-stilbene,
cyclohexene with 68% to 100% conversion and 41% to 88% selectivity toward the corresponding
epoxides .The products were analyzed by GC and GC-Mass. No desorption was observed during the
course of reactions.
Keywords: Cobalt complexes, Immobilization, Al-MCM-41, Epoxidation, Molecular Oxygen
196
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P-327
Synthesis of primary carbamates using H3PW12O40 as efficient catalyst under solventfree conditions
N. Jamadi and H. Aliyan*
Carbamates (urethanes) compounds spread out over a large area in nature, and their act of
applying to biologically active pharmaceuticals, agrochemicals, polymer industry and functional
materials are becoming to a larger and larger degree important. Several methods have been
developed for the preparation of these compounds. Most commonly used Lewis acids are Al(HSO4)3,
silicasulfuric acid (SSA) and other inorganic catalyst. However, all of these procedures suffer from
one or more of the following disadvantages such as long reaction times, low yields of the products,
harsh reaction conditions, the use of excess amounts of reagents, tedious workup procedures and
co-occurrence of several side reactions. In addition, some of the catalysts and reagents are
expensive, toxic and air sensitive. Therefore, there is still a need to search for better catalysts that
could be superior to the existing ones with regards to toxicity, handling and operational simplicity.
Herein, we wish to report a mild and efficient method for the preparation of primary carbamates in
the presence of catalytic amount of H3PW12O40 in room temperature under solvent-free conditions.
Keywords: primary carbamat, solvent-free conditions, polyoxometalates (POMs).
P-328
synthesis and characterization of rhodium complex with DAF (3,4-diamino- 1,2,5oxadiazole)
Jameh-Bozorghi.Sa * , Esfandiari.Hb , Khalili ghaydar.Hb
a
Department of Chemistry, Islamic Azad Univercity - Touyserkan Branch
e-mail : sjamehbozorgi@gmail
b
Department of Chemistry, Islamic Azad Univercity - Arak Branch
One important class of heterocyclic compounds for radiation chemical studies is furazan (1,2,5Oxadiazol) and its derivatives which, to our knowledge, have not been well explored. A practical
aspect of aminofurazans is the fact that diaminofurazan (3,4-diamino- 1,2,5-oxadiazole) suppresses
the burn rate and changes the pressure dependence of combustion of rocket propellants containing
NH4C1O4 oxidizer . 3,3΄-Diamino-4,4΄-azoxyfurazan (DAAF) has received major attention as an
insensitive high energy material of this class due to its positive heat of formation (+106 kcal/mol).
The synthesis and the experimental and theoretical characterization of rhodium complex with DAF
(3,4-diamino- 1,2,5-oxadiazole) is reported. 1H NMR, 13C NMR, IR-FT, UV–Vis and elemental
analysis are used to characterize the complex. Optimized molecular geometries in the gas phase at
the B3LYP/3-21G* and B3LYP/ LANL2DZ levels showed a distorted octahedral structure for
rhodium. All the calculations reported in this paper have been performed using the GAUSSIAN 03
(G03) program package. Geometry optimizations were carried out, without any symmetry
constraints, using both a polarized split-valence 3-21G* and a double-ζ LANL2DZ basis set with the
relative pseudopotential for the metal atom. The 1H NMR spectrum of the [Rh(DAF)(H2O)(Cl)3]
complex shows a singlet at 6.53 ppm indicating that the amine protons of the DAF ligand and the
13
C NMR shows a singlet at 149.68 ppm for this ligand.
Keywords: heterocyclic, furazan, rhodium complex, GAUSSIAN 03
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P-329
The Crystal Structure and Magnetic Properties of Tetra-k-methoxy-tetrakis[2-hydroxy-3
methoxybenzaldehyde (methanol)nickel(II)
A.H. Jamshidia, H. Keypoura*, R. Azadbakhtb and R.Golbedaghic
Faculty of Chemistry, Bu-Ali Sina University, Zip Code 65174, Hamedan, Iran
b
c
Department of Chemistry, Payame Noor University(PNU), Iran
The crystal structure of [Ni(OMe) (o-O.C6H4.CHO.OMe) (EtOH)]4 has been determined by threedimensional single - crystal X-ray methods. Four molecules of point symmetry 4 (S4) occupy a
tetragonal unit cell with a = 22-17 c = 9-70 A in space group /41/a. The four nickel atoms in the
molecule occupy the corners of a nearly regular tetrahedron with a bridging OMe group above each
face, giving a roughly cubic Ni۴0۴ unit of symmetry close to Td Approximately octahedral coordination of the nickel(II) ions is completed by four ethanol molecules and four chelated 2-hydr
oxy-3-methoxybenzaldehyde anions.
Keywords: Octahedral, Cubic Ni4O4 , Symmetry (S4).
P-330
Synthesis and Characterization of Ni(II),Cd(II),Cu(II) Oxo-Aza Schiff Base Complexes
A.H. Jamshidia, H. Keypoura* and R. Azadbakhtb
Faculty of Chemistry, Bu-Ali Sina University, Zip Code 65174, Hamedan, Iran
b
Department of Chemistry, payame Noor University, Hamedan, Iran
Schiff base complexes have been amongst the most widely udied coordination compounds in the
past few years.The variety of possible Schiff base metal complexes with a wide choice of ligands,
and coordination environments, has prompted us to undertake research in this area. N-(2-(2aminophenoxy) benzene-1,2-diamine is synthesized from reaction of 2-aminoethanol with 1-chloro2-nitrobenzene, and then reduction of the product by zinc dust and ammonium chloride. A novel
schiff base ligand is synthesized by reaction of N-(2-(2 aminophenoxy) benzene-1,2-diamine and 2hydr oxy-3-methoxybenzaldehyde in methanol. The corresponding complexes of nickel, copper and
cadmium were prepared. The complexes have been studied by IR and Mass spectroscopes.
Furthermore, cadmium complex was studied with NMR spectroscopy.
Keywords: Schiff Base Ligand, Nickel Complex, Cadmium Complex, Copper Complex, zinc dust.
198
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P-331
A novel coordination polymer with dicyanamide ligand: one dimensional architecture
stabilized by hydrogen bonding
Halimeh Janani a,*, Alireza Rezvani a, Ghobad Mansouri a Faramarz Rostami Charatib
b
Faculty of Science, Gonbad Higher Education Center, Gonbad, Iran.
Coordination polymers are a family of materials composed of 1D chains, 2D sheets, and 3D
networks of metal-organic building blocks connected via covalent and hydrogen bonds. Recently,
they have received considerable attention because of their wide applications in chemical separation
technologies and heterogeneous catalysis. In the present study, the synthesis, crystal structure,
detailed characterization and magnetic behavior of a new Cu (II) compound with the formula: [Cu
(acac) (phen) (dca)]. 2 H2O has been reported. Hydrogen bonds between both water molecules
creating a 1-D hydrogen bonded polymer. This complex characterized with CHN, FT-IR, 1H-NMR,
and UV-Vis spectroscopic method. The IR spectrum of this complex shows two strong bands at
1581 and 1520 cm-1That can be assigned to υ (C=O) and υ (C=C). Furthermore strong absorptions
are observed in the 2237–2209 cm-1 region corresponding to the combination modes of vibration of
the dca anion. Electronic spectrum exhibits the d-d transition at 632 nm. The absorption bands seen
in the UV region are assigned to (л-л*) transition. The effective magnetic moment (µeff = 1.95 B.M )
of complex was measured by Evans method. It is consistent with the µeff for Cu (II) complexes.
Keywords: Dicyanamide, Hydrogen bond, Cu (II) compound, Crystal structure
P-332
Synthesis, structure and magnetic behavior of a new double Azido bridge Cu (II)
complex
Halimeh Janania*, Alireza Rezvani a,,
Department of Chemistry, University of Sistan and Baluchestan, P. O. Box 98135-674,
Zahedan, Iran
Crystal engineering of coordination polymers based on pseudohalide ligands has been recently of
considerable interest. Pseudohalides are known as extremely versatile ligands in coordination
chemistry. They generate, as bridging ligands, a rich structural variety of polynuclear complexes
with interesting magnetic properties. The particular case of the azide anion is relevant in this
respect, since its bridging modes strongly influence the magnetic interactions between adjacent
metal ions, ranging from antiferro- to ferromagnetic couplings. In this paper, we report on the
syntheses, structural characterization and magnetic behavior of a new dinuclear complex with azido
bridges: [Cu (µ-N3) (C2N3) (phendione)] 2. The effective magnetic moment of the complex was
measured by Evans method on a 1H NMR Bruker DRX-500 MHZ, Avance spectrometer at ambient
temperature. In the IR the typical anion bands are observed at 2041 cm-1 for the azide stretching
vibration and for dicyanamide, vibrations are observed as strong bands at 2296, 2230, 939 and
1369 cm-1. The υ(C=O) was observed at 1577 cm-1. At 300 K µeff is 0.46 B.M it could also exhibit
the magnetic interaction between Cu (II) ions is antiferromagnetic. Electronic spectral data for this
complex in ethanol show the absorption bands in the UV region are assigned to ligand-centered
transitions (π π*).
Keywords: Magnetic interaction, Dinuclear, Azide, Bridging ligands
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P-333
Two new pseudo-halide bridged Cu (II) complexes with diimine ligands
Halimeh Janania* ,Alireza. Rezvani a
The pseudohalide dicyanamide anion may exhibit several coordination modes and govern
interesting chemistry in its coordination compounds. Until now as many as eight structurally
characterized coordination modes of dicyanamide had been reported in the literature. In most cases
dicyanamide is used to generate coordination polymers in the presence of other organic co-ligands
and it has been observed that the coordinating mode of dicyanamide ligand is largely influenced by
the nature of the co-ligands. Our study describes synthesis, characterization, spectroscopic and
magnetic behavior of two new copper (II) complexes with dicyanamide and diimine ligands. These
complexes [Cu (bipy) (µ-dca) (H2O) (NO3)] 2 (1) and [Cu (bpyam) (µ-dca) (H2O)]2 (NO3)2 (2) have
been synthesized and characterized with elemental analysis, FT-IR, 1H NMR, UV-Vis spectroscopic
and CV. The IR spectrum of complex 1 shows strong bands at 2277, 2193, 947 and 1338 cm-1
which are assigned to υas(C≡N), υs(C≡N), υs(C-N) and υas(C-N) respectively. These bands for
complex 2 are observed at 2242, 2183, 949 and 1350 cm-1. Electronic spectral data for these
complexes in ethanol show the absorption bands in the UV region are assigned to ligand-centered
transitions (π π*). µeff for complex 1 is 0.57 B.M. The present result shows the antiferromagnetic
coupling between copper (II) ions through the end-to-end dca bridge in the title complex.
Keywords: Pseudo halide, Diimine, Antiferromagnetic, Coordination modes
P-334
Antimicrobial and Anticancer Activity and Characterization of an Alkaloid as a natural
Ligand and its Fe (III) complex
a
b
c
A.Jarrah *, SH.Ghamamy ,R.malekfar
a
Department of chemistry , Islamic Azad university, Young researchers club, Ardabil Branch, Ardabil,
Iran , (e-mail:[email protected])
b
Dep. Chem., Fac. Sci., Imam Khomeini Int. Univ., Qazvin, Iran
c
Department of Biophysics, Faculty of Science, Tarbiat Modares University, Tehran, Iran
Morphine and its derivatives have received considerable attention as narcotic and used in lenitive
drudge
products. Morphine plays an important role in the therapy of acute and chronic pain. Exogenously
delivered morphine acts in the body by activating different subtypes of opioid receptors. Metal to
ligand complex with molecular formula [Fe (L)] Cl2, (L=codeine) of codeine as an alkaloid and its
iron complex have been prepared and characterized by elemental analysis,1HNMR, IR and UVVisible and Raman spectroscopy. The biological activity of alkaloids is believed to increase when
they are coordinated with transition metal ions. However, the literature on this subject is
contradictory and the outcome seems to largely depend on the experimental conditions. The results
of this analyze indicate that the complex has a Fe (III) ion coordinated via positions 4, 5-epoxy
(oxygen atom) and 6 of the codeine. The antimicrobial and anticancer activity of this complex was
studied and the codeine – Fe (III) complex 1 showed antibacterial and anticancer activities.
Keywords: codeine complex, Alkaloid, iron, antimicrobial activity, anticancer activity
200
IICC12
P-335
Synthesis and Characterization of New Complexes [R2Sn(C4H10N2)]2(R=Me٫Bu٫Ph) and
[R2Si(C4H10N2)]2(R=Me)
N.Jarrah and A.Tarassoli*
Department of Chemistry٫College of Sciences٫Shahid Chamran University٫ Ahvaz٫Iran
Organotin (IV) compounds are receiving increasing interest because of their potential applications
as bioactive agents ٫ especially those having Sn-N bonds. In this context ٫we studied the reaction of
piperazine (C4H10N2) with R2SnCl2(R=Me٫Bu٫Ph)in an inert atmosphere at different experimental
conditions . Piperazine is an intermediate material in the manufacture of insecticides٫rubber
chemicals ٫corrosion inhibitors and in the production of human and veterinary pharmaceuticals.The
new compounds were extensively studied by IR and multinuclear 1H٫13C٫119Sn nmr. In these
reactions the N-H protons have been removed and Sn-N bonds were formed and the reactions
leads to expected products. The yields were very good (70-90%) and the melting points were
around 200 to 210°c .The chemical shifts in 119Sn nmr spectra for these compounds were in the
range of chemical shifts suggested for Sn(IV) with coordination of four.Experiments were also
conducted to examine the reactions of dimethyldichlorosilane(Me2SiCl2) with piperazine in a similar
manner to obtain organosilicon compounds . The new compounds were characterized by 1H٫ 13C٫29Si
nmr as well as IR spectroscopy. In summary we have shown that the reaction of piperazine with
organosilicon or organotin chlorides led to the novel compounds containing Si-N or Sn-N bonds
which might have bioactive effects.
Keywords: organosilicon ٫ organotin ٫ piperzine ٫
119
Sn nmr spectroscopy ٫ 29Si nmr spectroscopy .
P-336
The effect of heterogeneous catalysts on oxidation and esterification of various alcohols
by K2FeO4
H. Javadi, M. Kooti* and A. Tarassoli
In this research work we have used wet chemical method for preparation of potassium ferrate
which includes the oxidation of iron (III) nitrate with an alkaline solution of hypochlorite. Then, this
reagent has been reacted with alcohols in conjunction with an appropriate heterogeneous catalyst
in n-hexane at room temperature. In order to find an efficient heterogeneous catalyst for K2FeO4,
we have examined the oxidizing abilities of various solid mixtures containing K2FeO4. Among the
mixtures: K2 Fe O4 – Al2 O3 – C u S O4.5 H2 O and K2FeO4 – CuSO4.5H2O, the mixture provided the best
results for oxidation and esterification of selected alcohols which are outlined below: 1. Oxidation
and esterification of α-phenyl ethanol, 4-chloro-1-phenyl ethanol and 1-phenyl propanol were
performed, with the solid mixture of K2FeO4-CuSO4.5H2O and, with the mole ratio of 3:2:1 with
good yield. 2. Oxidation and Esterification of 2-phenyl ethanol was performed with high yield
by the solid mixture K2FeO4-CuSO4.5H 2O and Al2O3 with the mole ratio of 3:3:1. In a similar
manner, benzyl alcohol, benzhydrol, 1-indanol, 2-octanol, cyclohexanol were efficiently
oxidized to their corresponding aldehydes or ketones. All the reactions were carried out at
room temperature and the progress of the reactions was monitored by TLC technique. In all cases
the resulted products were characterized by FTIR and 1HNMR and occasionally by 13CNMR
spectroscopy and comparing the spectra of the products with authentic samples.
Keywords: Potassium Ferrate, Heterogeneous Catalyst, Esterification, Oxidation
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201
P-337
Synthesis and Characterization of Some New Organometallic Complexes Obtained by
the Reaction of Bis (anilino) Phosphine Oxide with TiCl4 and Cp2ZrCl2
H. Javadi, A. Tarassoli*and M. kooti,
Phosph(V)azane derivatives have attracted special attention as an excellent ligands in the synthesis
of titanium and zirconium complexes, due to containing phosphorous, nitrogen and oxygen
heteroatoms. Unique properties of these compounds make some of them useful candidates for
catalytic and medical applications as well as precursors for the new polymer and sem-conductor
materials. Herein, bis (anilino) phosphine oxide was employed as a ligand for this synthesis. Then
the new organometallic complex, H(PhNH)P[(NPh)OZr(Cp)2Cl],(1) was prepared from the reaction
of ligand with zirconocene dichloride in the mole ratio of 1:1 in dry toluene. In a similar manner,
treatment of the ligand with zirconocene dichloride in the presence of tri ethyl amine and in the
mole ratio of 1:2:2 in dry toluene, yielded H(O)P[(NPh)2Zr(Cp)2], (2). Finally, the organometallic
binuclear complex, Cl3TiO(NPh)PH (NPh)PHO(NPh)TiCl3 (3), was produced from the reaction of bis
(anilino) phosphine oxide ligand with titanium tetrachloride in the presence of triethylamine and in
the mole ratio of 1:2:2 in THF–n–hexane (3:1). All the manipulations were carried out under
nitrogen, using standard Schlenk techniques. The newly obtained compounds were fully
characterized by elemental analysis, multi-nuclear NMR (1H , 31P , 13C), FT-IR spectroscopy, SEM
images and Uv-Vis spectrophotometry. On the basis of these results, bis (anilino) phosphine oxide
acts as a bidentate ligand and coordinates to the zirconium via (N , N) or (N , O) and titanium via
(N , O) atoms.
Keywords: Aminophosphine , Zirconocenedichloride , Bis(anilino)phosphine oxide,Coordination
chemistry
P-338
Synthesis and Reactivity of Two Fluoroantimonate Complexes(III):
Tetraalkylammonium Fluoroantimonate (R)4N[SbX3F], (R = C2H5, C4H9)
Z. Javanshir a,* and Sh. Ghammamy b
Department of Chemistry, Faculty of Science, young Reaserchers club, Islamic Azad Universit, ,
Ardabil Branch, Ardabil, Iran , E- mail: [email protected]
b
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
a
We had reported the synthesis of a number of fluorocompounds, with the belief that those reagents
could be used for the in catalysis of organic substrates. Two new ionic complexes of main metals
with tetrabutylammonium and tetraethylammonium cations were synthesized. One of them is
tetraethylammonium tetrafluoroantimonate(III), (C2H5)4N[SbF4] (TEATFA), that easily synthesized in
a nearly quantitative yield using a direct reaction of SbF3 and tetraethylammonium fluoride. Another
is tetrabutylammonium fluoroantimonate(III), [(C4H9)4N][SbF4], (TBATFA), that has been
synthesized by reaction of tetrabutylammonium fluoride with SbF3 salt. These compounds were
characterized by IR, UV/Visible, 19F NMR, 13C NMR and 1H NMR techniques. Production of these
compounds shows the ability of tetraethylammonium Fluoride and tetrabutylammonium Fluoride in
fluoride addition to transition metal and main group elements compounds.
Keywords: Antimony complexes, Fluorocomplexes, Synthesis, Characterization
202
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P-339
ZnO with Different Morphologies Synthesized by Solvothermal Methods
for Enhanced Photocatalytic Activity
Nasrin Talebian*, M.R. Nilforoushan, fateme Jazaeri
Iran
Pure hexagonal ZnO nanorods were synthesized by solvothermal treatment of zinc acetate in 20–60
wt.% hydrazine hydrate aqueous solutions as the solvent. The solvothermal method has been
successfully applied for the synthesis of various types of nanosized metal oxide with large surface
area, high crystallinity and high thermal stability. The products were characterized by means of
powder X-ray diffraction (XRD), scanning electron microscopy (SEM). It was found that the higher
content of hydrazine hydrate in the solvent can generally enhance the crystallinity of the obtained
ZnO powders. Photodegradation of intra crown orange, an azo dye was used as a model reaction to
test the photocatalytic activity of the ZnO samples. ZnO samples with different morphologies and
crystal growth habits exhibited different activities to azo dye degradation. The influence of the
content of hydrazine hydrate on the morphology of ZnO samples and the effect of the morphologies
on the photocatalytic activity are discussed.
Keywords: zinc oxide; solvothermal method; photocatalytic activity; X-ray diffraction; nanorod.
P-340
Nickel(II) complexes with phenyl cyanamaide derivatives as N-donor ligands
H. Chiniforoshan*,a,M. jazestania
a
Department of Chemistry,Isfahan university of thechnology,Isfahan,Iran
The coordination chemistry of phenylcyanamide ligands is expected to be as potentially rich as that
of the pseudohalides.However, very little has been done and it is only through recent efforts that
this chemistry is being elucidated. The attachment of a phenyl ring to the cyanamide group adds an
extra dimension not present in azide or thiocyanate ligands. An extensive_conjugation between the
cyanamide group and the phenyl ring provides an energetically favorable means by which a metal
ion can couple into a conjugated organic_ system. The recent interest in the field of inorganic
chemistry to develop novel hybrid materials that combine coordination and organic chemistry
provides further impetus to this research.The phenylcyanamides are ambidentate ligands whether
neutral or in anionic form and so the possibility of linkage isomerism must be recognized.The
aminenitrogen is sterically crowded by the phenyl ring and so terminal coordination to the nitrile is
expected, particularly for electron-rich metal centers. Metal ions that behave as acceptors are
expected to favor the anionic phenylcyanamide ligand in order to take advantage of the ligand’s
donor properties. In this study the ortho-substituted ligands such as halides and nitro
phenylcyanamides have been successfully synthesized and characterized by IR, UV–Vis
spectroscopy .Then the excess amount of these ligands added to nickel acetate .Finally we reported
the crystal structure of [Ni(L)2(H2O)4] where L is phenylcyanamide derivatives.
Keywords:
Phenylcyanamide
Ligands,Ortho-substituted
derivatives,Cyanamide
group,Nickel
acetate,Thiocyanate
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203
P-341
Synthesis, characterization and identification of wos3 cluster compounds with Ag+ and
Cu+ ions and heterocyclic thione ligand (Diaz)
(Diaz: 1, 3-diazinane-2-thione)
Bahar jeyhoon*, a, Reza Hyvadib ,Mohamad kootic
a
b
M.sc. Student Chemistry, Science and Research Branch,Islamic Azad University, Khuzestan, Iran
Department of Chemistry, Science and Research Branch,Islamic Azad University, Khuzestan, Iran
c
Department of Chemistry, Faculty of Science, Shahid Chamran University, Ahvaz, Iran
The reaction of thiometallate anions MOS3-2 (M=W, Mo) with d10metal ions and heterocyclic thione
ligands, the variety of compounds are obtained that are important from simulate to “Cu” and “Zn”
enzymes coordination active site of biological systems. Investigation of active site of copper(I)
enzymes and similarly for Ag(I) through simulation of active site of coordination is required for
which it is done with the use of thiometal compounds , thione ligands that contain nitrogen atom.
Modeling of enzymes has an important role in producing row materials with respect to the global
needs because we can obtain the method of different material by patterning Enzyme action cause
of their low environmental problems. By synthesis active coordination sites of copper’s enzymes, it
can invent a new method for synthesis of raw material in laboratory and industry and study their
acting mechanism. In this work we present the synthesis and structural characterization of two new
clusters contain [WOS3]-2 as a ligand to copper and silver from elemental analysis(C.H.N) and UVVis,FT-IR and 1H,13NMR spectroscopy. The reaction of AgI and CuCl with WOS3-2 and heterocyclic
thione ligand Diaz (1,3-diazinane-2-thione) in acetone or acetonitril solvent yields the cluster
complex [WOS3Ag3(Diaz)3I] and [WOS3Cu3(Diaz)3Cl],that have been characterized by various
spectroscopies and (C.H.N).
Key words: Cluster, Thiometal, Heterocyclic thione, Diaz, Tungsten complexes.
P-342
Transition Metal (Hg(II), Ag(I) and Cd(II)) Complexes of Some New Phosphorus Ylides
S. Javad Sabounchei a*, Vida Jodaian b* and Hassan Nemattalaba
a
b
Phosphorus ylides are important reagents in organic chemistry, especially in the synthesis of
naturally occurring products with biological and pharmacological activities. The utility of metalated
phosphorus ylides in synthetic chemistry has been well documented. Reaction of two new
phosphorus ylides Ph3PCHCOC10H7 (Y1) and Ph3PCHCOC4H3S (Y2) with mercury (II) halides and a
previously reported ylide (p- tolyl)3PCHCOOCH2Ph (Y3) with CdCl2 in equimolar ratios using
methanol as solvent yielded binuclear complexes of the type [(Y).HgX2]2 (Y=Y1 and Y2, X=Cl, Br and
I) and a complex of [(Y3).HgCl2]2. The latter ylide reacts with Hg(NO3)2.H2O in the same solvent
with equimolar ratios to give a polynuclear complex [Hg(Y3)(NO3)(µ-NO3)]n. Also, the reaction
between ylides and AgNO3 in 1:2 molar ratios gave mononuclear complexes. Characterization of
these products was carried out by elemental analysis, IR and multinuclear NMR techniques.
Keywords: Phosphorus ylides, triphenylphosphine, mercury(II) nitrate, silver nitrate.
204
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P-343
Synthesis and multinuclear NMR study of some new Ag (I) complexes containing the
ligands 4-methoxybenzoylmethylenetriphenylphosphorane and
furylmethylenetriphenylphosphorane
Seyyed Javad sabounchei a and Vida Jodaian b
b
a
The preparation and characterisation of α-stabilised phosphorus ylides, and metal complexes
incorporating these ylides, has attracted much attention in recent years. Phosphorus ylides are
important reagents in organic chemistry, especially in the synthesis of naturally-occurring products
with biological and pharmacological activities. The utility of metalated phosphorus ylides in synthetic
chemistry has been well documented. Juxtaposition of the keto group and carbanion in phosphorus
ylides allows for the resonance delocalization of the ylidic electron density while providing additional
stabilization to the ylide species. The α-keto-stabilized phosphorus ylides R3P=C(R’)COR” (R, R’ and
R” = alkyl or aryl groups) show interesting properties such as their high stability and their
ambidentate character as ligands (C- versus O-coordination). The reactions of the title ylides,
{(C6H5)3PCHCOC6H4OCH3)} (MBPPY) and {(C6H5)3PCHCOC4H3O)} (FPPY) with silver (I) nitrate in 1:2
ratios using dichloromethane as solvent have yielded mononuclear complexes of the type
[(MBPPY)2. Ag] NO3 and [(FPPY)2. Ag] NO3. The ylide and its complexes were characterized by
elemental analysis as well as IR and multinuclear NMR techniques
KEYWORDS: phosphorus ylide, silver (I) nitrate complexes, triphenylphosphine.
P-344
Surface modification of TiO2 to improve its adsorption capacity
M. Jouybar, M.A. Zanjanchi *, M. Arvand
Adsorption techniques are widely used to remove certain classes of pollutants from wastewaters. In
this work the adsorption characteristics of surfactant-modified TiO2 was investigated. TiO2
nanostructures have been synthesized by means of a simple hydrothermal method using TiCl4 as
titanium source and EtOH/water mixture. The physicochemical features of the TiO2 nanostructures
were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy, BET surface area measurement
(BET) and infrared spectroscopy (IR). The adsorption characteristics of sodium dodecyl sulfate
(SDS) on TiO2 (SDS-TiO2) were studied in detail. TiO2 was found to be an efficient adsorbent for
SDS and could be used for the removal of methylene blue as a prob pollutant from wastewater. For
comparison, the MB adsorption was carried out on Degussa P25 TiO2 suspensions under the same
condition. Batch studies were performed to evaluate the effects of various experimental parameters
such as contact time, adsorbent dose, initial MB concentration, and pH on the removal of the dye.
Equilibrium isotherms for the adsorption of MB were analyzed by Freundlich and Langmuir isotherm
models. The obtained results showed that the adsorption of the MB dyes on a hybrid Inorganicorganic material can be performed with a high efficiency.
Keywords: TiO2 nanoparticles; Surfactant; Methylene blue; Adsorption; SDS;
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205
P-345
Catalytic Activity of β-Halogenated Mn-Porphyrins in the Oxidation of Alcohols using
Tetrabutylammonium Peroxomonosulfate
a
S. Kaafi Mashhadi, A. Rezaeifard*, M. Jafarpour
Synthetic manganese porphyrins are remarkably active mimics for cytochromes P450, ligninases,
and superoxide dismutases. Their catalytic efficiency in these biomimetic systems is usually related
to the metal-centered reduction potential, a property that may be conveniently tuned by the
appropriate design of the porphyrin ligand. β-Halogenated manganese porphyrins comprise the
third generationof porphyrin-based catalysts and are among the most efficient catalytic systems. In
this study, different factors that may affect the reactivity of oxidation of alcohols using
tetrabutylammonium Peroxomonosulfate catalyzed by Mn(III)(BrxPP)Cl (x = 0,2,3,4) in the
presence of nitrogenous axial bases as co-catalysts have been investigated. The strong π-donor N–
H imidazoles displayed co-catalytic activities greater than strong σ-donor amines and weak π-donor
pyridines. According to the TOF/min and TON/24h of the oxidation reactions, a lower catalytic
activity but higher stability was observed for β-brominated catalysts than non-brominated one. The
catalytic efficiency correlates with the degree of β-bromination and the best results were achieved
with the tetrabrominated complex.
Keywords: Halogenated Porphyrin, Oxidation, Alcohol, Peroxomonosulfate, Catalytic activity.
P-346
New cyclophosphazane: synthesis, characterization, strructure determination and
Peridiction of biological activity
a
Kh. Gholivand *a, A.A.Kalateh a, S. Movassaghi b
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115 – 175, Tehran, Iran.
b
Corresponding Author E-mail: [email protected]
The chemistry of small inorganic hetrocycles of the type (P-N)2 are of great interest in resent
researches, mainly because such mulecules are good straining materials for poly syclic inorganic
and organometallic compounds. The wide range application of cyclophosphazanes in nucleophilic
subsituation reactions on P-Cl bonds, coordination chemistry, and ring opening polymerization
reactions causes a significant attraction to this area of chemistry. Investigations on
cyclophosphazane are an important part of phosphoramidate chemistry due to their synthetic,
structural, coordination and biological applications. These molecules have anticancer properties
which biological activity predicted with PASS software. Herein, we have considered the synthesis
and
spectroscopic
characterization
of
new
cyclophosphazane
with
formula
[C6H11NH]P(O)[NC6H11]2P(O)[NHC6H11] was prepared according to the Scheme 1. The structure of
compound was caracterized by 1H, 13C, 31P NMR, IR, and mass spectroscopy. The ione molecular
peak and fragmentation in Mass spectrum in Scheme 2 approved this structure (m/s=483).
Keywords: cyclophosphazane, cyclohexylamine, Spectra characterization, Theoretical technique,
PASS.
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P-347
Synthesis of lead oxide nanoparticles by sol-gel method
M.Karamia, M.M.kashani-Motlaghb,*
b,*
a
Our goal in this research was to obtain lead oxide nanoparticles by sol-gel method. This method is
the first time used to synthesize lead oxide nanoparticles. These nanoparticles are useful in
pigments and active materials of lead-acid batteries. In this method, lead oxide nanoparticles were
synthesized through the reaction of citric acid solution as stabilizer and lead acetate solution as
precursor. At first, in the presence of lead acetate and citric acid, transparent sol was obtained, and
then the transparent sol was transformed into a dry gel in the oven. Finally, the dry gel was
calcinated at different temperatures for 12h. The effects of different parameters including
calcination temperature and the ratio of citric acid to lead acetate were investigated. The prepared
lead oxide nanoparticles were characterized by IR, X-ray diffraction (XRD) and scanning electron
microscopy (SEM).
Keywords: sol-gel; nanoparticles; PbO.
P-348
Synthesis of four Mn (II) complexes with L-Lysine and L-Histidine and characterization
of them by infrared spectroscopy
F.Karami Shirazi ,H. A.Rasekh* ,Gh.Gholami
Department of Chemistry ,Islamic Azad University of Firooz Abad-Branch
[Mn (L-Lys)2 (H20)2] SO4.11H2O, [Mn(L-Lys)2 ( H2O)2] (NO3)2. 15H2O , [Mn (L-His)2 (H2O)2 ] SO4
.9H2O and [Mn (L-His)2 (H2O)2] (NO3)2 . XH2O (L-Lys: L-Lysine, L-Hys: L-Hystidine ) were
synthesized in aqueous solution and characterized by IR spectroscopy. In this complexes L-Lys and
L-His formed chelate ring. In the IR spectra a broad band in region 2600 – 3600 cm-1 shows a lot
of number of H2O molecules in all four complexes . A sharp peak in 1626 – 1628 cm-1 observed due
to asymmetric stretching vibration of C=O band and a peak in 1416 cm-1 observed for symmetric
stretching vibration of C=O band . A peak in 1330 cm-1 observed due to stretching vibration of C-O
band. Asymmetric and symmetric bending vibration of N-H band observed in 1600 cm-1 and 1500
cm-1 region ,respectively .The sulfate counter ion observed in the medium peak in 1100 cm-1 and a
weak peak in 800 cm-1. The nitrate has normally a peak at 1384 cm-1 was split here in two bands.
Keywords: synthesis, complex, infrared, L-Lysine, L-Histidine, Mn(II) complexes.
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P-349
Zeolite encapsulated Heteropoly acid as an Efficient catalyst for
tetrahydropyranylation of alcohols and phenols
Reihaneh Kardanpour, *Shahram Tangestaninejad, Majid Moghadam, Valliolah Mirkhani, Iraj
Mohammadpoor-Baltork, Ahmad Reza Khosropour
E-mail*: [email protected]
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan, 81746-73441, Iran
The protection of hydroxyl groups has found widespread application especially in steroids, sugars,
glycerides and natural products. It is also useful for multi-step organic syntheses. The
tetrahydropyranylation is one of the most frequently employed methods to protect hydroxyl group
of alcohols and phenols. The THP ethers are attractive because they are less expensive and are
stable enough to a variety of condition. A wide variety of catalysts already been applied for
tetrahydropyranylation of alcohols and phenols including the use of protic acids, Lewis acids, ion
exchange resins and etc. In this work heteropoly acid encapsulated in zeolite Y was prepared and
characterized by FT-IR, X-ray diffraction (XRD), differential thermal gravimetry (DTG) techniques.
This catalyst was used for tetrahydropyranylation of alcohols and phenols at room temperature. In
this catalytic system primary, secondary and tertiary alcohols and phenols were converted to their
corresponding tetrahydropyranyl ether in excellent yield. At the end of each reaction, the catalyst
was filtered, washed and dried at 120 C for 2 h. No appreciable loss in the catalytic activity of the
catalyst was observed after reusing the catalyst for four consecutive runs.
Keywords: Tetrahydropyranylation; Polyoxometalate; Zeolite
P-350
Synthesis of a New Series of trans-[CoIII(Me2bpb)(amine)(N3)].H2O Complexes;
Characterization and Electrochemical Investigation
Fatemeh Karimia, Soraia Meghdadia, Mehdi Amirnasr*a, Kurt Mereiterb, Ahmad Amiria
b
Faculty of Chemistry, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna,
Austria
a
Metal complexes of many amido ligands have been extensively used to mimic the properties of
biologically active systems. In this context, metal complexes of a wide variety of picolinamide–
based ligands have been studied as structural and/or functional models of several metalloproteins.
In this study, we describe the synthesis and characterization of complexes of the type trans[CoIII(Me2bpb)(amine)(N3)] {Me2bpb2- =N,N’-(4,5-dimethyl-1,2-phenylene) dipicolinamide and amine
= pyridine (py), 4-methylpyridine (4-Mepy), 4-acyl pyridine (4-Acyl) and N-methyl imidazole (NMeIm). The complexes have been characterized by elemental analyses, IR, UV-Vis, and 1H-NMR
spectroscopy. The crystal structure of [CoIII(Me2bpb)(py)(N3)].H2O has been determined by X-ray
crystallography. The cobalt(III) center resides in a distorted octahedral environment with the
Me2bpb2– ligand occupying the equatorial plane of the octahedron. The remaining coordination sites
are occupied by the pyridine and azide ligands in trans position. The electrochemical behavior of
these complexes with the goal of evaluating the structural effects on the redox properties has been
studied.
Keywords: Carboxamide, Cyclic Voltammetry, Cobalt (III) Complexes, X-ray Crystallography.
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P-351
Synthesis and catalytic properties in olefin epoxidation of dioxomolybdenum (VI)
complex bearing a bidentate 4-methyl-1,2-phenylenediamine ligand
R.R.Khojasth*, G.karimi Nik, S.D.Mir Ahmadi
Department of chemistry , North Tehran Branch , Islamic Azad
University , Tehran , Iran
Epoxides are important organic intermediates since they undergo ring-opening reations with a
variety of reagents to give mono or bi-functional organic products. One of the preferred methods of
epoxide synthesis is the reaction of olefins with hydrogen peroxide or alkyl hydroperoxides,
catalysed by transition metal Complexes . Molybdenum catalysts are very versatile in olefin
epoxidation and are the basis of important industrial processes for the epoxidation of propylene
with alkyl hydroperoxides as the oxygen source. Reaction of MoO2 (acac)2 {acac=acetylacetonato}
with 4- methyl-1,2-phyenylenediamine produced an interesting stereo structure which studied
different aspects of this synthesis, and the complex were found to oxidize allyl alcohol to their
oxides. The structure of the product was examined by 1H, 13C-NMR,IR spectroscopy and elemental
analysis.
Keywords: dioxomolybdenum (VI) catalyst , 4-methyl-1,2- phenylenediamine, olefin epoxidation.
P-352
Application of Ammonium decatungstocerat as an Efficient Catalyst for the Formation
and Deprotection of Tetrahydropyranyl Ethers
a
D. Karimiana*, V. Mirkhania, B. Yadollahia, I. Mohammadpoor-Baltorka
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441, Iran
It should be noted that polyoxometalates (POMs) take into consideration because of their properties
and applications in recent years. In such compounds, due to the high amount of oxygen atoms, the
metal atoms are used in their highest oxidation state, which cause the significant oxidizing and
Lewis acid capability for these compounds. According to this fact, this class of inorganic compounds
can be used as acid and oxidation catalysts. In the most of organic reactions a multifunctional
compounds can be used, while one of these functional groups have to takes part into the reaction.
In this respect, other groups have to be protected against reacting. It goes from saying that the
protected group needs to be deprotected to get the final product. The common way for protecting
of OH functional group is using 3,4-dihydro-2H-pyran (DHP), which cause the formation of
tetrahydropyranyl (THP) ethers from respective alcohol. Since these protection/deprotection
reactions takes long time and be carried out in severe condition, it bears in mind that it is necessary
to apply an appropriate catalyst for performing these reactions. Along the same line, we want to
focus on synthesis of Cerium containing polyoxometalate and using of it in catalytic synthesis of
tetrahydropyranyl ethers and their deprotection. According to the capabilities of this catalyst, we
use it in protection/deprotection of variety of alcohols/ethers under the ambient condition. A
significant result in terms of the time and yield of the reaction was observed.
Keywords: Polyoxometalate, Cerium, Tetrahydropyranyl ethers, Protection, Deprotection
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209
P-353
Structural Determination of Platinum(II) complexes with bidentate ligands
a,b
Sima kavanda, Saeed Dehghanpourb*
The crystal structure of platinum (II) complexe [PtCl2L] (L = (4-chlorophenyl)pyridin-2ylmethyleneamine) was determined using single crystal X-ray diffraction. The complexe undergo
stacking to form a zigzag Pt···Pt···Pt chain containing both short 3.62(8) Å and long 5.41(9) Å
Pt···Pt separations through the crystal. Factors such as the steric, electronic, and conformational
interactions influence the spectroscopic properties of platinum(II) complexes and modify their redox
potential, which are important in practical applications. Compound crystallizes with two molecules
per asymmetric unit (molecule A and B) showing some conformational differences. The crystal
structure of complex 2 consists of monomeric cis-[Pt(B)Cl2] molecules. The Pt center has typical
square planar geometry in which the largest deviation from the mean coordination plane is 0.089(2)
Å (in N1a) and -0.064(2) Å (in N1b), very similar to that of [Pt(A)Cl2]. The phenyl groups are
slightly twisted with respect to these moieties. In the structure, the platinum–platinum vector is
inclined by 14.15(9) Å with respect to the coordination plane. The platinum atoms are shifted
2.34(1) Å towards the ligand in the a direction. As a consequence, the molecules no longer overlap
with the halogen ligands sandwiched between the chelate planes and vice versa, but there are
partially overlapping ligands with a nearest distance between the parallel pyridine planes of 3.09(2)
Å. Again, the molecules stack in the b direction in a head to tail fashion with two different PtּּּPt
distances. In this arrangement, the short PtּּּPt distance is 3.62(8) Å. The second PtּּּPt
distance is much longer (5.41(9) Å) and PtּּּPt ּּּPt chain angle is 113.91(2)°.
Keywords: platinum (II) complexe, bidentate ligands, X-ray,crystal structure
P-354
NiCl2 an efficient catalyzed for Baeyer–Villiger oxidation of ketones
by NaOCl
N. O. Mahmoodia,* K. Kazemib
a
b
University of Azad Islamic, Rasht Branch, Iran
Many traditional oxidation processes are associated with the use of stoichiometric high-oxidationstate transition metals, hazardous solvents and the production of large volumes of toxic waste.
Therefore, there is an increasing interest in catalytic systems able to perform these reactions in a
more industrial scale, using cheap reagents, oxidants and solvents. The Baeyer–Villiger oxidation of
ketones is a reaction of considerable interest in organic chemistry because the products, lactones or
esters, are important synthetic intermediates in the agrochemical, fragrance chemistry and chemical
and pharmaceutical industries. The reaction can be catalyzed by acid, base, enzyme, or transition
metal-containing materials. Herein we report the facile oxidation, using rather inexpensive and
commonly available reagents. The oxidation proceeds rapidly in the presence of nickel(II)chloride
salts and excess bleach under ambient conditions and appears to be quite general, giving
predictable products with high yields (70-95%) and high purities in most cases. This reaction is
chemoselective while the reaction preformed in the presence of excess catalyst. In this
circumstance the glutaric acid is an sole product with almost 100% yield conversion.
Keywords: Baeyer–Villiger reaction, NiCl2, Lactone.
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P-355
A General, simple and efficient RuCl3. n H2O- catalyzed direct alkylation of active
methylene compounds with benzylic alcohols
under mild conditions
F. Kazemi Rad, K.Tabatabaeian, A. Fallah Shojaee , F. Shirini
Department of chemistry, University of Guilan, Rasht, Iran
Alkylation of active methylene compounds, such as β-diketones, β-diketoesters and malonic esters
is a very important transformation in organic synthesis which has been investigated extensively.
Generally, this transformation is carried out using alkyl halides in the presence of a stoichiometric
amount of base. Although this method works well even on large scale, often it is associated with
significant drawbacks including nonavailability and toxicity of halogenated substrates, the use of
strong base and production of large amounts of salts as by-products. Therefore, the development
of a practical and economical process for carbon–carbon bond formation between active methylene
compounds and unmodified substrates is an important task. Various CH-acidic 1,3-dicarbonyl
compounds react with benzylic alcohols to give the corresponding 2- benzylated products in
efficient yield. Typically, reactions proceed under mild conditions in the presence of catalytic
amounts of Ruthenium trichloride hydrate.
Keywords: Ruthenium trichloride hydrate, Active methylene compounds, Alcohols
P-356
Characterization of different manganese-oxo porphyrins complexes by UV.vis
spectrophotometer
Ahmad Keshavarzi, Zahra Solati*, Leila Ebrahimi
Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran
In manganese porphyrin complexes, co-catalysts belived to play crucial roles in generating the
intermediate oxygenating species and tuninig their reactivities.The intervention of several
intermediates, namely oxomanganese (IV) porphyrin (por MnIVO),oxomanganese (V) porphyrin
(porMnvO) have been postulated for porMnIII catalyzed oxidations. It has been demonstrated that in
all of these systems, MnIII(oxidant) adduct is created that in some cases directly transfer the oxygen
atom to the substrates. In this work, we report the changes in the visible spectra during the
reaction of Mn(TPFPP)Cl and Mn(TPP)Cl with n-Bu4NHSO5 and m-CPBA in the presence of various
n-Bu4NX salts (X=F,Cl ,Br) as co-catalysts at room temperature in CH2Cl2. The UV.vis spectroscopy
studies revealed the formation of various manganese-oxo intermediates with different stability and
reactivity.
Keywords: Manganese Porphyrins- Tetra butylammonium salts- tetra-nbutyl ammonium hydrogen
monopersulfate- Meta chloro per benzoic acid
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211
P-357
Ultrasonic-assisted Method for One-pot Synthesis of β-Hydroxy Ketone Derivatives
using RuIII-BINAP
a
The development of a catalytic system that is able to catalyze stereoselective reactions in good
yield is a true challenge. One concern of the synthetic organic chemist is to develop new
asymmetric catalytic methodologies using transition metal complexes. In this field, several groups
have focused their research on the development of ruthenium catalytic reactions. On the other
hand, chiral ligands have been successfully employed in a number of transition metal-catalyzed
asymmetric transformations. The most versatile, and consequently most investigated, ligand is the
BINAP ligand. It can be coupled to many transition metals, and it catalyzes a wide range of
asymmetric reactions. Recently, we have reported an efficient protocol for the cross aldol reaction
in the presence of RuCl3.nH2O/(S)-BINAP. Encouraged by these results, we reinvestigated the same
synthetic protocol, using ultrasonic irradiation to overcome the problem of somehow prolonged
reaction times. A mixture of aldehyde and ketone under the influence of catalytic amounts of
RuCl3.nH2O, BINAP and KOH was irradiated with ultrasound in a sealed tube at room temperature
(checked by TLC) to give aldol adducts as the main products. These results revealed the promotion
of the aldol reaction by ultrasonic irradiation. All products were characterized by 1H NMR, 13C NMR
and IR data. With this new catalytic promoting system, various aldehydes were coupled to generate
diastereoselective products. The reaction is versatile and also offers several advantages, such as
shorter reaction times, cleaner reaction profiles and simple experimental and work-up procedures.
Keywords: Ruthenium catalyst, BINAP, Ultrasonic irradiation, Aldol reaction
P-358
Regioselective Synthesis of Progesterone Derivatives using RuCl3.nH2O as a
Homogeneous Catalyst
a
RuIII salts are well known to catalyze a variety of organic transformation, including Michael
reactions, oxidation reactions of alkanes, oxidative cyanation of amines, and many others. We have
recently reported the aldol reactions, using catalytic amounts of RuIII, and the investigation of the
chemistry of ruthenium continues to be one of the most active areas of organometallic chemistry.
On the other hand, progesterone is one of the most important hormones of the steroidal pregnane
series. It also helps to create a balance of all other steroids and has intrinsic calming and diuretic
properties. Thus, due to the importance of progesterones to the human body and in continuation of
our previous works on aldol reactions, we would like to report the formation of β-hydroxy ketone
derivatives derived from it. Treatment of progesterone with aldehydes in the presence of
RuCl3.nH2O (5.5 mol%) along with KOH in dioxane at room temperature, gave the corresponding
aldol adducts in good yields with complete diastereoselectivities. The results show the catalytic role
of RuCl3.nH2O at room temperature in the regioselective aldol reaction between progesterone and a
series of aldehydes. From an operational viewpoint, the reactions do not require an inert
atmosphere, and can be performed over a short period of times without preactivation of the donor
substrates (direct aldol reaction). The products were characterized by 1H NMR, 13C NMR and IR
data.
Keywords: RuIII salt, Aldolization, Regioselective, Hormone steroid.
212
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P-359
Hydrothermal synthesis of Nb (V) Doped Li2Si2O5 nanolayers
Sh.Khademinia, A.A.Alemi*, E.Ghavidel, Y.Hanifehpour
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz,Iran.
Because of hardness and corrosion stability, Niobium is used for preparing alloy and steel and used
in superconductors and electronic and optic. Niobium is a paramagnetic metal and causes electricity
conduction with doping in a material. In this research work Li2-xNbxSi2O5 was synthesized that
with x=0.01 mol% Nb5+ XRD patterns indicate that is isostructural with Li2Si2O5. For synthesis
doped lithium disilicate LiNO3, SiO2.xH2O, Nb2O5, NaOH were used as raw materials and the
reaction performed in steel autoclave in 180oC and for 96 h. The summery of the reaction is shown
in figure 1. SEM shows the morphology change of lithium disilicate upon doping of Nb5+ ions into
lithium sites from separate nanolayers to nanoteplates. The FTIR spectrum shows the infrared
properties of Nb doped lithium disilicate. The unit cell of Li2Si2O5 crystal is Orthorhombic crystal
system with space group: Ccc2, α=β=γ=90oC, a=5.807, b=14.582, c=4.773 according to the x-ray
diffraction data. The schematic of this synthesis has been shown below in figure1. Summery of
Li1.98Nb0.01Si2O5 with hydrothermal reaction in 180oC for 96 h reaction time. n summary,
Li2Si2O5 nanolayers were synthesized by hydrothermal method at180°C and the morphology
changes of the materials were discussed.
Keywords: Lithium Disilicate, Hydrothermal, XRD Pattern, Nanolayers, Niobium, Doping.
P-360
Preparation and characterization of Sb6O13 nanocrystals by hydrothermal method
Sh. Khademinia, A.A. Alemi*, E. Ghavidel, Y. Hanifehpour
Antimony oxide with defect pyrochlore structure (Sb6O13) crystallize in the cubic system with space
group Fd3m. Antimony oxide often promotes the activating catalysts used for selective partial
oxidations and for reactions such as oxidative coupling. Antimony oxide can be used as a catalyst,
retardant, fining agent and optical material. Thoroughly mixtures of antimony oxide (Sb2O3) and
cerium nitrate (Ce(NO3)3.6H2O) used as a starting materials. In a typical procedure, Sb2O3 (0.291g)
and Ce(NO3)3.6H2O (0.434g) were dissolved into 10 ml of distilled water at room temperature in
beaker and magnetically stirred to obtaining homogeneous solution. The as-obtained product was
transferred into a Teflon lined stainless autoclave. The autoclave was sealed and maintained at
180°C for 48h.The XRD patterns of the synthesized Sb6O13 were indexed to a cubic phase with
lattice parameters of a=10.2963Å that undertaken with celeref software. The intensity and position
of the peaks are in good agreement with the values reported in the literature. To study time effect
on optical properties, the experiment was carried out in different times (24h, 48h). The Sb6O13
prepared in 24h shows high quantum yield than Sb6O13 prepared in 48 and Band gap for Sb6O13 is
2ev. In summary, Sb6O13 nanocrystals were synthesized by hydrothermal method at180°c. cerium
oxide acts as a auxiliary function and catalytic factor.
Keywords: Antimony Oxide, Hydrothermal, XRD, Optical Properties
IICC12
213
P-361
Synthesis of Li2SiO3 nanoparticles via Hydrothermal method
Sh.Khademinia, A.A.Alemi*, Y. Hanifehpour
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz,Iran.
Li2SiO3 presents an orthorhombic crystal structure with Ccm21 space group. The synthesis of lithium
silicates have been carried out using different methods, including sol–gel, precipitation, extrusion–
spherodisation process, rotating melting procedures, combustion and solid-state reaction. The final
products contained Li2SiO3, Li2Si2O5, Li4SiO4, and quartz. In this research work synthesis of lithium
metasilicate nano particles via hydrothermal method and XRD, FTIR and SEM analysis of obtained
materials has been studied. Synthesis of Lithium metasilicate nanoparticles were performed via
hydrothermal method at 180°C in different reaction times. In this research work, LiNO3, SiO2.xH2O
and NaOH were used as raw materials. XRD phase analysis and FTIR spectroscopy spectra
confirmed the synthesis of Li2SiO3 nano particles. The 1:2 molar ratios of Li: Si was used to
synthesize Li2SiO3 in 48, 72 and 96 hour reaction times. When the time was changed, the
morphology of nano particles lent forward to compact sheets and then to the flower like structure.
The SEM pictures have shown these results and have been confirmed by XRD phase analysis. The
synthesis of Li2SiO3 nano particles was performed by hydrothermal reaction in low temperature
180°C. FT-IR, XRD and SEM were used to analysis the structure characteristics of Li2SiO3
nanocrystals.
Key words: Lithium Metasilicate, Hydrothermal, Nanoparticles, XRD Pattern.
P-362
The synthesis and characterization of trinuclear copper(II) complexes
Batoll Khaledi and Rasoul Vafazadeh*
There has been considerable interest in synthesising trinuclear copper(II) complexes. These
trinuclear copper(II) complexes are important as models for the active sites of multicopper proteins,
like ascorbate oxidase, ceruplasmin and laccase. A new trinuclear (homo- or heteronuclear)
complexes, Cu(II)M(II) Cu(II) M = Cu, Zn and Sr, have been synthesized by reaction of Cu(salpn)
complex, salpn is N,N'-propylen-bis(salicylaldimine) with MX2 (X = Cl and NO3) in methanol solution
(2:1 mole ratio) resulted in the formation of green complexes (Figure 1). These complexes have
been characterized by IR, UV-Vis spectroscopy and elemental analyses. The analytical data of CHN,
lead to postulate [(Cu(salpn))2MX2] empirical formulae for the trinuclear complexes. The electronic
spectra of the complexes were recorded in methanol solution. Single absorption bands about at
600-610 nm in visible region are observed that indicate typical d-d transition in the square-planar
environment around Cu(II).In addition, IR spectra of Cu(salpn) and the trinuclear complexes in
comparison with the IR spectrum of the free ligand, the strong υ(C=N) band Cu(salpn) and the
trinuclear complexes are shifted towards lower frequencies compared to that of the free Schiff base
ligand, reflecting the coordination of the ligand to metal centers.
Key words: copper(II) complexes, trinuclear, homonuclear, heteronuclear, Schiff base
214
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P-363
Synthesis of iron-nanosilicte (mesopore)and adsorption efficiency of heavy metals
P. Khalesia,*, H.Sepehrianb, A.Khalesic, A.Malekynejada and M. Manochehri a
Department of chemistry, University of Islamic Azad. Central Tehran Branch, Tehran, Iran
b
Nuclear science and technology research institute, AEOI, P.O. Box11365/8486, Tehran, Iran
c
Department of chemical Engineering, Iran University of science and Technology, Tehran, Iran
a
Heavy metals are one of the most important pollutants in surface water. These metals have been
found in industrial west water that must be removed. In this research iron nanosilicte (mesopore)
polymer absorbent production methods has been investigated. Also, absorption efficiency of heavy
metals has been considered. Herein, waste water PH and residence time have been optimized. In
this study mesoporous MCM-41, Fe-MCM-41 have been prepared in various condition with
cetyltrimethylammonium bromide (C16) and dodecyltrimethyl-ammonium chloride as template and
characterized by power X-ray diffraction, N2 adsorption–desorption measurements.
Keywords: Nanosilicate polymer, Adsorbent, Heavy metal, West water, MCM-41.
P-364
Synthesis, Spectral Studies and Thermal Behavior of Three Organotin(IV)
Complexes with an ONS-donor Ligand: 3-Methoxysalicylaldehyde
thiosemicarbazone
M. khandania, T. Sedaghatb,*, M. Kootib
Department of Chemistry, Science and Research Branch, Islamic Azad University of
Khuzestan, Ahvaz, Iran
a
b
Interest in complexes of both main group and transition metals with sulfur donor ligands arises
from their varied structures and biological activity. In recent years much attention have been paid
to the synthesis, characterization, biological activities and industrial application of various
organotin(IV) derivatives with sulfur donor ligands like thiones or dithiocarbamates. The Schiff base
compounds derived from thiosemicarbazide through condensation with various aldehyde and
ketones have emerged as an important class of sulfur donor ligands because of their mixed hardsoft donor character, versatile coordination behavior and pronounced biological activity. In this
reaserch work, organotin (IV) chlorides R2SnCL2 (R=Ph, Me, Bu) react with a thiosemicarbazide
ligand (H2L) obtained from condensation of thiosemicarbazide and 2-hydroxy-3methoxybenzaldahyde. Spectral properties of new complexes were investigated by IR, 1H NMR ,13C
NMR and 119Sn NMR spectroscopy and show that in the three complexes H2L acts as a tridentate
dianionic ligand and coordinates to the metal with an ONS-donor set from phenolic oxygen, imine
nitrogen and thiol sulfur, respectively. 119Sn NMR data are consistent with the presence of fivecoordinate tin(IV) in solution. Also thermal decomposition of the complexes has been studied by
thermogravimetry.
Keywords: Thiolates, Thiosemicarbazide, thermogravimetry, Organotin(IV)
IICC12
215
P-365
Synthesis, characterization and electronic spectroscopy of copper (II) and cobalt(II)
complexes with a N2O5 donor Schiff base ligand.
A. A. khandar*, f. Shahbazi, S. A. Hosseini Yazdi
Faculty of chemistry, Tabriz University, Tabriz, Iran
Email address: [email protected]
Schiff base ligands and their complexes derived from the reaction of derivative salicylaldehyde and
various amines have been extensively used to synthesized many complexes of Cu (II), Ni (II) and
Co (II). Copper(II) and cobalt(II) complexes of N2O5 schiff base ligand H3L: 1 2,2'-(1Z,1'Z)-(2,2'-(2hydroxypropane-1,3-diyl) bis(oxy) bis(2,1-phenylene)) bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1ylidene) diphenol prepared of salicylaldehyde and diamine 1,3-bis(2-aminophenoxy)propan-2-ol (1)
were synthesized and characterized by elemental analyses, IR, molar conductivity and electronic
spectroscopy.
Keywords: Schiff
salicylaldehyde
base;
Copper(II)
complexes;
Cobalt(II)
complexes;;
X-ray
structure;
P-366
Synthesis and studies of Schiff base ligands with N4O2 donors and
its complexes with Co(II) and Zn(II) ions
A.A.Khandar*, T.Taghavee, S.A.Hosseini-Yazdi,
Faculty of chemistry,Tabriz University,Tabriz,Iran
In the present research work,the ligands 1,2-di [N-2-phenoxy-pyrrol-2-carboxaldimine] ethane (H2L1)
and 1,4-di [N-2-phenoxy-pyrrol-2-carboxaldimine] butane (H2L2), were prepared by condensation
reaction of pyrrol-2- carboxaldehyde with 1,2-di (o-amino phenoxy) ethane and 1,4-di (o-amino
phenoxy) buthane, respectively. Reaction of H2L1, H2L2, with Cobalt (II) and Zinc (II) acetate salts
result in ML1, ML2, complexes ( M= Co,Zn). The synthesized ligands and their complexes have been
characterized by elemental analysis, Uv-visible, IR, 1H NMR, 13C NMR spectroscopy.
Keywords: Schiff base, Pyrrol-2-carboxaldehyde derivatives, Co(II) and Zn(II) complexes.
216
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P-367
1-D mercury(II) porous coordination polymers with multidentate Schiff-base ligand
A. A. Khandar*, G.mahmoudi
Faculty of Chemistry, Tabriz University, Tabriz, Iran
During the past 20 years, the field of coordination polymer research has become an extremely
prolific area of chemistry. Coordination polymers have been studied widely as they represent an
important interface between synthetic chemistry and materials science, as having specific
structures, properties, and reactivities that are not found in mononuclear compounds. Here we
report 1-D mercury (II) porous coordination polymers with multidentate Schiff-base ligands. the VTXRD study shows water molecules have important role in stability of crystal structure. Below picture
showing the solvate channels in the crystal structure.
Keywords: porous coordination polymer, VT-XRD, multidentate Schiff-base ligand.
P-368
Synthesis, characterization and biological activity of copper(II) complexes of 1,2,4triazole- based ligands
Hamid Khanmohammadia,*, Fakhr-o-sadat Mirnezamia, Ahmad Hamtab
a
[email protected]
b
Department of Biology, University of Arak, Arak, Iran
The development in field of bioinorganic chemistry has increased the interest in Schiff base
complexes, since it has been recognized that many of these complexes may serve as models for
biologically important species. Schiff bases derived from various heterocycles were reported to
possess cytotoxic, anticonvulsant, anticancer and antifungal actives. Among the plethora of
hetercycle-based Schiff bases, those containing 1,2,4-triazole are of particular interest. The
incorporation of 1,2,4-triazole into macroacyclic ligands has facilitated the isolation of a wide range
of transition-metal complexes with interesting electrochemical, biological and magnetic. In this
report, a series of Schiff base ligands H2Ln (n=1-3) were synthesized by condensation reaction of 5pyridyl-4-amino-3-mercapto-4-H-1,2,4-triazole and salicylaldehyde derivatives. The Cu(II)
complexes of the prepared ligands were synthesized by in situ reaction of HA and salicylaldehyde
derivatives in the presence of Cu(ClO4)2.6H2O. The ligands and their complexes have been
characterized by elemental analysis and spectroscopic methods. The investigation of antibacterial
screening data revealed that all tested free ligands did not show any antibacterial activity against E.
coli and S. aureus as gram negative and positive bacteria but the Cu(II) complexes show
antibacterial activities against S. aureus as gram positive bacteria.
Keywords: Schiff base, 1,2,4-Triazole, Copper(II) complexes, Biological activity
IICC12
217
P-369
Nano perovskite SrCoO3 as Catalyst for model exhaust gas oxidation
M. Khazaia, A. Malekzadea,*, Y. Mortazavib and A. Khodadadib
Department of Chemistry, University of Damghan, Damghan, I. R. Iran.
b
Catalysis and Nanostructured Materials Research Laboratory, Department of Chemical Engineering,
University of Tehran, Tehran, Iran
a
Mixed metal oxides are comprised the vast majority of catalysts and are used in modern chemical
industry. Perovskites structure with the ABO3 formula form an interesting category of mixed metal
oxides, studied widely in view of their activity in complete oxidation, thermal stability and relatively
low costs. Perovskites are also considered of great interest as the environmentally friendly and
cheap catalyst. Nano perovskite SrCoO3 was prepared by the citrate method in which citric acid was
added to emulsify the mixture. Catalysts were prepared by drying of a solution, containing
appropriate concentration of metal nitrate and citric acid equal to 0.0, 1.0, 2.5 and 5.0 times of the
total number of mole of nitrate ion. Dried powder was calcined at 900oC for 5 h. Prepared samples
were characterized by the FTIR, XRD, SEM and EDS analysis. The performance test of the samples
was carried out for oxidation of a model exhaust gas containing 6.0%CO and 0.2%C2H6 in Ar mixed
with stoichiometric amount of air. Ethane was selected as a model for unburned hydrocarbons in
exhaust gas. The SrCoO3 nano perovskite with addition of citric acid equal 2.5 times of the nitrate
ion is observe to be a better catalyst with the highest performance in lower temperature for
oxidation.
Keywords: Nanocatalyst, Perovskite, Emulsifier, SrCoO3, Exhaust gas, CO oxidation, unburned
hydrocarbons.
P-370
Catalytic oxidation of hydrocarbons with oxovanadium(v) complex
Samaneh kheirabadi and Hassan hosseini monfared*
Department of Chemistry, Zanjan University 45195-313, Zanjan, Islamic Republic of Iran. Email:
[email protected]
Schiff bases play an important role in inorganic chemistry as they easily form stable complexes with
most transition metal ions. The oxidation of hydrocarbons with Schiff base complexes has been a
field of academic and industrial interest to analyze the catalytic activity of various metal complexes.
The development in the field of bioinorganic chemistry has increased the interest in Schiff base
complexes, since it has been recognized that many of these complexes may serve as models for
biologically important species. Saturated hydrocarbons, alkanes, are known to exhibit only very low
reactivity in reactions with variety of normal reagents and in many cases the yields of the products
are negligible. In last decades, new methods of alkane functionalization with participation of various
transition metal complexes in solutions have been discovered and developed. Among these
reactions, catalytic oxidations of alkanes under mild conditions are especially interesting both from
practical and academic point of view. In this study, we have synthesized an active oxovanadium
complex with benzhydrazone Schiff base ligand and investigated its catalytic activity in oxidation of
alkanes with aqueous 30% hydrogen peroxide. This catalyst was able to oxidize various alkanes
with good to excellent conversion in mild conditions.
Key words: Oxidation, Hydrogen peroxide, Hydrazone Schiff base, Vanadium complex.
218
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P-371
Synthesis and characterization of new Cd (П) complexes contaning azo-azomethine
ligands
F. khodam, H. Khanmohammadi*
[email protected]* E-mail:
Schiff bases offer a versatile and flexible series of ligands.capable to bind with transition, non
transition metal ions to give complex with the suitable properties for theoretical and practical
application .Schiff bases and their complexes have important properties such as the catalytic
oxidation reaction ,redox systems in biological processes, degradation of dyes through
decomposition of hydration peroxide and other reagents, intextile industries. In the present work
new schiff base ligands synthesized by condensation reaction of 1,3-bis((aminoethyl)thio)benzene
with various azo-coupled 1-(3-formyl-4-hydroxy phenyl azo)-4chlorobenzen. The prepared ligands
were allowed to react with Cd (П) ion in the molar ratio (1:2:ligand:metal ion ) at THF solution .The
structures of the ligands and their metal complexes were characterized by spectroscopic methods (
IR , 1H NMR ,UV-VIS ) and elemental analysis.
Key words: azo-azomethine, schiff base, 1H NMR, complexe
P-372
Efficient and facile method for synthesis of phthalans catalyzed by nano carbon solid acid
Z. Khorsandi, A. R. Khosropour,* V. Mirkhani,* I. Mohammdpoor-Baltork, M. Moghadam, S.
Tangestaninejad
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan, 81746-73441 Iran
The phthalan (1,3-dihydroisobenzofuran) structure as an important scaffold have been widespread
used for the synthesis of complex molecules. Moreover, some derivatives of them have some
biological or pharmacological importance. On the other hand, Phthalan derivatives are utilized in the
agricultural industry as herbicides or fungicides and in other industries as colorants and perfumes.
Recently some limited methods have been reported for the synthesis of these compounds.
However, these methods have some disadvantages such as long reaction times, low yields and
utilizing toxic reagents. So, designing of benign procedure for this synthesis is too important. In this
work we wish to demonstrate an efficient and eco-friendly protocol for the one-pot synthesis of
phthalans catalyzed by nano carbon solid acid, based on Oxa-Picted-Spengler reaction. Novel and
reusability of the catalyst could be considered as other advantages of this procedure.
Keywords: phthalan, nano carbon solid acid, heterocyclic synthesis, Oxa-Picted-Spengler reaction
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219
P-373
Ruthenium Catalyzed Synthesis of 6H-indolo[2,3-b]-quinolines
a
Indoloquinoline alkaloids have interesting biological activities. Indolquinoline alkaloid rich plants
have been used to treat a variety of disorders including malaria, rheumatism and other diseases.
Recently, we have been involved in the study of catalytic potential of Ruthenium as a homogeneous
catalyst. Indoles, on the other hand, contribute in many biologically active compounds, and are of
great interest in the synthetic community. The investigation of the chemistry of indoles has been,
and continues to be, one of the most active areas of heterocyclic chemistry. Here, we report a
convenient method for preparation of 6H-indolo[2,3-b]-quinolines, starting from indoles and amines
catalyzed by ruthenium. The present protocol provides an easy route to heterocyclic structures
related to alkaloids.
Keywords: Indoloquinoline, Alkaloid, Ruthenium, Indole.
P-374
Ruthenium Catalyzed Conversion of Hydrocortisone to Corresponding 17-Ketosteroid
a
Hormone steroids are members of the large family of steroids, and play a vital role in a wide variety
of essential physiological processes including cell growth, maintenance of salt balance and sugar
metabolism. They have also been implicated in responses to stress and sexual imprinting of the
fetal brain. Abnormalities in steroid hormone synthesis, metabolism and receptor interaction
contribute to a variety of diseases. Synthetic steroids are used extensively in fertility control, as
anti-inflammatory agents and immunosuppressants. Hence, derivatization of steroids is still an
active area of investigation. Here, we report a convenient conversion of hydrocortisone to
corresponding 17-ketosteroid using ruthenium as a homogeneous catalyst.
Keywords: Corticosteroids, Ruthenium, Catalysis, Hormone.
220
IICC12
P-375
Heterogeneous Ruthenium-Based Catalyst for Preparation of Indole Derivatives
a
The development of new, efficient synthetic methods leading to indole derivatives continues to
receive much attention in organic synthesis because of the biological activities of indole derivatives.
Bis(indolyl)methanes passes a wide range of biological activity and their synthesis has received a
considerable amount of interest. We have recently reported an efficient method for preparation of
BIMs using Ruthenium chloride hydrate as an efficient homogeneous catalyst. Heterogeneous
catalytic systems offer several advantages such as ease of work-up, recycling, thermal stability, and
so on. Here we report Ru (III) exchanged Zeolite Y as an efficient and recyclable catalyst in the
condensation of indoles with ketones under mild reaction conditions.
Keywords: Heterogeneous, Catalyst, Ruthenium, Indoles.
P-376
Diastereoselective Ag/BINAP Catalyzed Addition of Indoles to Symmetric Enones
a
β-indolylketones have received much attention as important building blocks for the synthesis of
many natural products and other biologically active compounds. Over the past few years, many
synthetic methods for preparation of these compounds have been reported. However, relatively less
attention has been paid to the double-conjugate 1,4-addition of indoles to symmetric enones
leading to di(indol-3-yl) derivatives. We have recently reported such double-conjugate additions
using ruthenium as a homogeneous catalyst. However, the reported procedure suffered from the
lack of diastereoselectivity. Here we report a chiral, silver based catalyst in improving the
diastereomeric ratio. The results revealed that high selectivity could be obtained, by using a chiral
auxiliary.
Keywords: Catalysis, Silver, BINAP, Indole.
IICC12
221
P-377
An efficient one-pot synthesis of tetrahydrobenzo[a]xanthene-11-one using RuCl3.nH2O
as homogeneous catalyst
M. Khoshnood Jalalia, K. Tabatabaeianb *, M. Mamaghanic
a
Member of Young Researchers Club, Rasht Branch, Rasht, Iran
a,b,c
Many organic transformations which involve organometallic ruthenium species as catalyst are
known and well documented. RuIII salts are well known to catalyze a variety of organic
transformations, including aldol and Michael reactions, oxidation reactions of alkanes, and many
others. Xanthenes are important biologically active heterocyclic compounds, which possess antiviral,
anti-inflammatory and antibacterial activities. Furthermore, these compounds can be used as dyes
and in laser technologies. Herein, we are reporting the reaction of aldehydes, 2-naphthol and
dimedone for the formation of tetrahydrobenzo[a]xanthene-11-one in presence of catalytic amount
of RuCl3.nH2O under reflux conditions in ethanol as solvent. All the products are known compounds
and were characterized by melting point and IR spectroscopic data. A test reaction using 4hydroxybenzaldehyde, 2-naphthol and dimedone without any catalyst was performed and was
found that only 10% conversion to product was obtained even after 2.5 h of heating. Therefore, we
have developed an efficient and environmentally benign methodology for the synthesis of 12-aryl 8,
9, 10, 12-tetrahydrobenzo[a]xanthene-11-ones by a one-pot, multi-component reaction. The
advantages of this method are reduced reaction times, higher yields, mild reaction condition, and
easy purification.
Keywords: Xanthene; Aldehyde; Ruthenium catalyzed reaction; 2-Naphthol.
P-378
RuCl3.nH2O as an efficient catalyst for the synthesis of xanthene compounds
M. Khoshnood Jalalia, K. Tabatabaeianb *, M. Mamaghanic
a
Member of Young Researchers Club, Rasht Branch, Rasht, Iran
a,b,c
Ruthenium complexes demonstrate a variety of useful characteristics, which include low redox
potential, high electron transfer ability, high coordination ability to heteroatoms, Lewis acid acidity,
unique reactivity of metallic species and intermediates such as oxo-metals, metallacycles, and metal
carbene complexes. Therefore, a large number of novel, useful reactions have begun to be
developed using catalytic amounts of ruthenium complexes. Among oxygenated heterocyclic
compounds, xanthene and its derivatives are particularly important for different reasons such as
biologic and treatment properties (antivirus and antibacterial). These compounds are the main
source of a big group of natural material to imagine biomolecules and because of their spectrum
properties; they are used in dyes and laser technology. Herein, we are reporting the reaction of
aromatic aldehydes and resorcinol for the formation of 9H-xanthene-3,6-diols in presence of
catalytic amount of RuCl3.nH2O under reflux conditions in methanol as solvent. All the products are
known compounds and were characterized by melting point and IR spectroscopic data. The present
method offers several advantages such as excellent yields, short reaction time, mild condition, and
simple work-up.
Keywords: Xanthene-3,6-diol; Aldehyde; Ruthenium catalyzed reaction; Resorcinol.
222
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P-379
Synthesis and Solvatochromic Studies of Mixed-Chelate Copper(II) Complex
F. khoshsiar, H. Golchoubian,*, S.Tobarary and M. Sabbaghian
(e-mail: [email protected], e-mail: [email protected]
Solvatochromic phenomenon in the mixed-chelates metal complexes has received great attention
because they may be used as a Lewis acid-base color indicator and also utilizes to develop optical
sensor materials to monitor pollutant levels in the environment. In this work the synthesis and
solvatochromic behaviour of a new mixed-chelate copper(II) complexes with the general formula
[Cu(Cl-acac)(diam)]ClO4 in which diam = N,N-bis((furan-2-yl)methyl)ethane-1,2-diamine and Clacac = 3-chloropentane-2,4-dione as shown in Scheme 1, were studied. The electronic absorption
spectra of the complex were measured in the solution state in some organic solvents with different
donor number (DN). The donor number expresses a measure of coordinating ability of solvent on
the standard of that of dichloroethane (DCE). The complex showed positive solvatochromism.
Spectroscopic studies of these complexes demonstrated that in solid state ClO4- ions are bound
weakly above and below of the chelate plane. However, in solution perchlorate ions are driven out
by solvent molecules leading to their solvatochromism. Regression analysis of band maxima of
these compounds against donor number of solvents indicated good correlation and also confirms
the solvatochromic behavior of these complexes.
Keywords: Synthesis, Solvatochromism, Diamine, Mixed-chelate, Copper (II) complex.
P-380
Application of natural Western Azarbaijan Zeolite for removal of inorganic compounds
from waste water
Amir Khosravi *, Majid Esmhosseini, Atallah Bahrami, Somayeh Khezri
Department of Chemistry, Faculty of Science, Urmia University,Urmia, Iran
*E _mail: [email protected]
Heavy metals are toxic priority pollutants that commonly interfere with the beneficial use of
wastewater for domestic and industrial application. Furthermore, Nitrogen in the Ammonium form
can have deleterious effects in water resources. Therefore removal of inorganic contaminants
mentioned from wastewater would have vital importance for protection of public health. The most
widely used method of removing inorganic compounds from wastewater is ion exchange process.
Zeolites with their high cation exchange ability as well as to the molecular sieve properties have
been used as adsorbents in ion exchange process. The purpose of this study was to investigate the
possibility of the utilization of natural Western Azarbaijan Zeolite for removal of heavy metal ions
(Pb2+, Cd2+) and Ammonium ion (NH4+) from waste water by ion exchange. Both batch and
continuous experiments were carried out .The effects of relevant parameters, such as initial
concentration, stirring time, pH and dosage of absorbent at room temperature on removal efficiency
completely were investigated.It was observed that removal efficiency can achieve higher than 98%.
The results show that natural Western Azarbaijan Zeolite has appropriate cation exchange capacity
can be used for removal Ammonium and heavy metals from effluents and applied as a new
adsorbent for treatment wastewater.
Keywords: Inorganic compounds removal; Natural Western Azarbijan Zeolite ; Ion exchange;
Waste water
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223
P-381
Synthesis and characterization of Co2+ and Mn2+ complexes whit tridentate hydrazone
Schiff bases
F. Khosravia , B. Shaabanib,*, E. Farajzadeha , N. hajizadeha , R. Shafiee zadeha , E. Nikjooa , S.
Baghbania , M.Khansoltania
a
b
Schiff bases play an important role in inorganic chemistry as they easily form stable complexes with
most transition metal ions. The development in the field of bioinorganic chemistry has increased the
interest in Schiff base complexes, since it has been recognized that many of these complexes may
serve as models for biologically important species. The remarkable biological activity of acid
hydrazides R–CO–NH–NH2, a class of Schiff base, their corresponding aroylhydrazones and the
dependence of their mode of chelation with transition metal ions present in the living system have
been of significant interest. The coordination compounds of aroylhydrazones have been reported to
act as enzyme inhibitors and are useful due to their pharmaco-logical applications.In this work we
report the synthesis and characterization of tridentate Schiff-base ligand from the reaction of 3hydroxy-2-naphthohydrazied with 2-hydroxy-1-naphthaldehyde, Figure 1, and its complexes with
Co2+ and Mn2+ cations. The complexes were characterized with IR, Uv/Vis and conductance
measurements.Comparison of spectroscopic results for the ligand and complexes and also visible
absorption spectra for complexes suggest that ligands act as tridentate and coordinates via two
oxygen, carbonyl and hydroxy ogxygenes, and imine nitrogen atoms.
Keywords: Schiff-base, Tridentate, Transition metal cations
P-382
Preparation and characterization of catalytic beds supported with hetero-poly acids and
their application in catalytic reactions
M. Khosravi, M. Mirzaee,*, B. Bahramian and M. Faghani
Department of Chemistry, Shahrood University of Technology, Shahrood, semnan, Iran
The extensive application of supported heteropolyacids (HPAs) as a heterogeneous catalyst for a
wide variety of applications continues to thrive. Acidity of the HPAs for certain catalytic reactions
can be adjusted by choosing a suitable support. Apparently, besides the surface area, particle size,
pore structure and distribution of the protons of HPAs, which are usually referred to as the
elements of tertiary structure, the nature of supports and interaction of HPAs with support is very
influential on catalytic activity. In this research we have been investigated catalytic activity of
different HPAs (H3PW12O40, H4SiW12O40) supported on different metal oxide powders (ZnO, TiO2,
ZrO2) in some organic reaction such as esterification of benzyl alcohol with acetic acid. Supporting
of HPAs on metal oxide surfaces and the yield of organic reactions were investigated by Uv-Vis
Spectroscopy and GC respectively.
Keywords: Heteropolyacid, Heterogeneous catalyst, Catalytic bed, Organic reaction.
224
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P-383
Synthesis and Characterization of new bisamide ligands containing N,N- bis (2quinoline carboxamide)-2,6 diamino pyridine and their complexes
N. Khosravi, A. Zamanpour*
Department of Chemistry, Islamic Azad University, Firoozabad branch, Iran
A large variety of pyridine amide ligands have been synthesized for investigating their metal-binding
properties, for use in catalysis, and as molecular receptors. Polynuclear transition metal complexes
containing nitrogen donor atoms are of considerable interest in inorganic and biomimetic chemistry
due to their potential application in catalysis, their biological relevance, and potentially interesting
magnetic properties. Metals maybe part of the active sites of enzymes, stabilize the macromolecular
structure of proteins and effect enzymes or membranes to control cell metabolism. Macrocycles
containing quinoline side arm have found many applications as analytical reagent in absorptions
spectrophotometery, solvent extractions, these compounds are also used as pesticides. Ligands that
contain amide moieties stems from their occurrence in metalloproteinase and metal complexes of
glycopeptides antibiotics like blomycine. A new novel potentially pentadentate ligand, N,N bis (2quinoline carboxamide)2,6 diamino pyridine have been synthesized by reaction of 2,6 diamino
pyridine and quinaldic acid. The peptide group –C (O) NH- is an important construction unit in
chemistry and biology. Then, Cu(II), Ni(II) and Co(II) complexes of this ligand have been
synthesized and characterized by IR, UV-Vis, element analyses and 1HNMR spectroscopy. This
complex coordinated to the nitrogen atom of the two deprotonated amides and the central pyridine,
and the two nitrogen of the quinoline.
Keyword: Macrocycles, Quinoline, Quinaldic acid, Peptide group, Synthesis.
P-384
Synthesis and spectroscopic characterization of molecular complexes of mesotetraarylporphyrins with NbCl5
Z. Sabourifard, H. Dehghani*
Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Iranِِ
Recently, there has been considerable interest in the study of electron donor-acceptor (EDA)
complexes between macrocyclic ligands and a variety of acceptor molecules. Among different
macrocyclic ligands used for EDA complexation, the porphyrins which have been extensively studied
as photosynthetic mimics, photodynamic therapy agents, electrocatalysts and DNA binding agents.
Porphyrin are known since the beginning of 1960s, even during the recent decay, general interest
has been attract toward the investigation of chemical properties, methods and reactions of
synthesis, and new applications of these macromolecules. In this study, several substituted mesotetraarylporphyrins H2T(X)PP (X=H, 4-CH3, 4-OCH3,4-CH(CH3)2 have been prepared, and reacted
with NbCl5 for formation of [H2T(X)PP(NbCl5)] molecular complexes. In the complexes UV-Vis and
1
H NMR spectroscopic data showed the porphyrins are distorted so they can easily bonded to
acceptors with the loan pair electron of pyrrolenine nitrogens. The results showed that two lone
electron pairs of pyrrolenine nitrogens in the porphyrins act as σ-electron donors, to the empty
orbitals of central atom in NbCl5 for formation of the molecular complexes. This work shows that
meso-tetraphenylporphyrins react with NbCl5 and give 1:1 (acceptor:donor) molecular complexes.
H2T(X)PP + NbCl5 → [H2T(X)PP(NbCl5)]
Keywords: Molecular Complex, Porphyrin, NbCl5, Electron donor, Electron donor, Electron
acceptor.
IICC12
225
P-385
Novel complexes of Hg(II) with 1,10-Phenanthroline and 2,2'-bipyridine Derivative
Ligands; Synthesis, Characterization and Crystal Structure Determination
a
A. Khosrojerdya, R. Alizadeha,*
School of chemistry, Damghan university, Damghan, Iran
*
Various dimensional infinite molecular coordination assemblies have been the subject of great
interest in recent years owing to their potential application in catalysis, optical properties,
clathration, etc. The d10 metals are promising for fabricating such coordination assemblies due to
their wide variety of coordination numbers and geometries. Hg (II) complexes remain much less
explored. Metal ion complexes with bidentate ligands continue to be of strong interest in many
areas of chemistry. Ligands based on the 2,2′-bipyridine (bpy) and the o-phenanthroline
frameworks have played a particularly important role because of the imbedded π-electron system
present. Their complexes with metal ions spanning much of the periodic table have led to a wide
variety of systems with interesting structural, spectroscopic, catalytic, biomimetic, properties. In
present work two mercury (II) complexes with Ph2phen (1) and dmbpy (2) (where Ph2phen is 4,7diphenyl-1,10-phenanthroline and dmbpy is 6,6′-dimethyl-2,2′-bipyridine) were synthesized from
the reaction of Hg(SCN)2 with Ph2phen and dmbpy. Both complexes were thoroughly characterized
by elemental analysis, IR, 1H and 13C NMR spectroscopy and single-crystal X-ray diffraction
methods.
Keywords:
bipyridine.
Crystal
Structure,
Hg(II),
4,7-Diphenyl-1,10-Phenanthroline,
6,6′-Dimethyl-2,2′-
P-386
Synthesis and characterization of Co(II), Ni(II) and Mn(II) bi-nuclear complexes of
hexadentate (ONO)2 Schiff base ligand
Mehrnosh Kiani a,*, A.H. Kianfar b and farahnaz mohammadloa
Department of Chemistry, Islamic Azad University of Gachsaran Branch,
b
Department of Chemistry, University of kohgiloyeh boyerahmad, Yasouj ,Iran
a
The chemistry of Schiff bases is a field that is being noticed. These compounds and their metal
complexes had a variety of applications, including biological, clinical, analytical, and industrial. They
also play important roles in catalysis. 4,6-Diacetylresorcinol serves as a starting matrial for the
generation of multidentate symmetrical Schiff bases. In this work neutral hexadentate (ONO)2 type
bi-nuclear complexes of Co(OAC)2.4H2O, Ni(OAC)2.4H2O and Mn(OAC)2.4H2O have been synthesised
using a Schiff base formed by the condensation of 2-amino phenol in a molar ratio 2:1 with 4,6Diacetylresorcinol (The method of preparation of 4,6-Diacetylresorcinol (DAR) was as cited in the
literature) in methanol. Structure of the ligand and all the complexes were characterized on the
basis of their micro analytical data, elemental analysis, melting points, IR,1H NMR and UV–Vis
spectra. The infrared spectrum of the complexes under investigation confirmed the site of chelation,
hence, the complexes showed strong absorptions due to ν(C=N) and ν(C—O). The above
absorptions have been shifted on complexation confirming the chelation positions.
Keywords: Schiff base ligand; bi-nuclear complexes; 4,6-Diacetylresorcinol; 2-amino phenol
226
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P-387
Preparation and characterization of Ni2P/CNTs Nanocatalysts for hydrodesulfurization
(HDS) of naphtha
a
M. Kiania, H.R. Aghabozorgb* and A.M. Rashidib
Faculty of chemistry, Islamic Azad University-North Tehran Branch, Tehran, Iran
b
Research Institute of Petroleum Industry, Tehran, Iran
(e-mail: [email protected] and [email protected])
Sulfur removal from petroleum feed stocks is becoming one of the most significant issues in the
refinery industry because of recently enacted environmental protection laws. Therefore, many
reports are published about the preparation of proper catalyst for desulfurization of hydrocarbon
fuels. In this work, Ni2P catalysts supported on carbon Nanotubes (CNTs) are prepared by
temperature programmed reduction through a novel method using nickel (II) dihydrogenphosphite
as a precursor salt with different nickel loadings on the carbon nanotubes denoted as Ni2P-x, where
x is the percentage of the active phase. The prepared samples are characterized by X-ray diffraction
(XRD), scanning electron microscopy (SEM), tunneling electron microscopy (TEM), FT-IR and
surface area measurement using BET method. The catalytic activity of the prepared catalysts was
studied in hydrodesulfurization of naphtha. The results indicate that Ni2P Nanocatalyst shows better
activities than conventional catalysts because of their large surface area. The conversion hardly
changes with the metallic loadings and increases with temperature in all cases. On the other hand,
Ni2P-10/CNTs catalyst shows a better intrinsic activity of Ni2P phase.
Keywords: Nickel phosphide, Carbon nanotubes, Hydrodesulfurization, Naphtha
P-388
Synthesis, Characterization, X-ray Crystallographic Structural Study and Catalytic
Properties of a Nickel(II) Schiff base complex
M. Koliaeia, S. Rayatib,* and H. R. Khavasic
Department of Chemistry, Payame Noor University, P. O. Box 68158-348, Khorramabad, Iran
c
Department of Chemistry, Shahid Beheshti University, Evin, Tehran 1983963113, Iran
a
b
Schiff bases and their transition metal complexes are of significant current interest even though
they have been prepared for decades. They have been used in various applications such as
catalysis, corrosion protection, and molecular sensors. Nickel Schiff base complexes have been
established to be some of the most versatile catalysts for oxygenation reactions. In the present
research, a Ni(II) Schiff base complex has been synthesized and characterized by elemental
analyses, infrared and 1H NMR spectroscopy and single-crystal X-ray diffraction analysis. This
complex used as catalysts for oxidation of cyclooctene and styrene with tert-butylhydroperoxide
(TBHP). Oxidation of cyclooctene with TBHP gave cyclooctene oxide as the sole product, but in the
case of styrene a mixture of styrene oxide and benzaldehyde has been obtained in ca. 1:3 molar
ratio. Also, various parameters such as solvent, temperature and concentration of oxidant have
been optimized.
Keywords: Nickel(II), Catalyst, Oxidation, Alkene.
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P-389
Synthesis and Characterization of New Complexes Resulting of the Reaction of R2SnCl2
(R=Me٫Bu٫Ph)and R2SiCl2 (R=Me) with 2٫2´‫ـ‬Oxydiethanethiol
A. Kord and A. Tarassoli*
Department of chemistry٫College of science٫ Shahid Chamran University٫ahvaz٫ Iran
Organotin (IV) complexes form an important class of compounds٫ not only because of tin based
anti-tumour drugs٫but also owing to industrial and agricultural applications. The most widely used
ligands in the formation of complexes are those which can establish Sn-S bonds. Therefore٫ the
bidentate disulfide ligand 2٫2´‫ـ‬oxydiethanethiol is an interesting ligand to be studied in the
coordination reaction of organotin halids.In this research project٫R2SnCl2(R=Me٫Bu٫Ph) is reacted
with 2٫2´‫ـ‬oxydiethanethiol in the ratio of 1:1 in benzene at the present of sodium ethoxide.The
resulting products were extensively characterized by 1H٫13C and 119Sn nmr and IR spectroscopy.The
absence of SH peak at 2658 cm-1 in IR spectrum and the signal at δ=2.1 ppm due to SH proton in
nmr is indicating the elimination of protons and the formation of Sn-S bonds.The 119Sn nmr exhibit
the Sn signal at δ=85 ppm. This chemical shift confirms that the coordination number of Sn is
four.The suggested structure of the new compounds is [R2SnO(CH2CH2S)2]2.Finally the reaction of
dimethyldichlorosilane with 2٫2´‫ـ‬oxydiethanethiol is carried out in a similar manner and the new
products were isolated and characterized by IR spectrophotometry and 1H٫13C٫29Si spectroscopy.In
conclusion٫ this research study is described synthesis and characterizan of some new organosilicon
and organotin compounds.
Keywords: 2٫2´‫ـ‬oxydiethanethiol ٫organosilicon ٫organotin٫29Si nmr spectroscopy٫119Sn nmr
spectroscopy
P-390
Synthesis and characterization of manganese 5, 10, 15, 20-tetrakis (4benzylamin)porphyrin and immobilization of the complex to polymer for investigation
of its catalytic activity in oxidation reactions
S. Kowkabi, G. R. Karimipour*
Department of Chemistry, Yasouj University, Yasouj 75918-74831, Iran
Tetrapyrrolic macrocyles namely porphyrins and their derivatives have been described as
appropriate model for cytochrome P-450 enzymes. These macrocycle ligands are prepared by the
condensation of pyrrole and aldehyde in the presence of an acid catalyst and oxidant. In this work,
we report the reduction of 5, 10, 15, 20-tetrakis (4-cyanophenyl)porphyrin to 5, 10, 15, 20tetrakis(4-benzylamine)porphyrin by lithium aluminum hydride in the presence of sodium hydroxide
in low temperture. Also, supporting the porphyrin complex on organic polymer in the presence of
acryloye chloride as a substance that convert 5, 10, 15, 20-tetrakis(4-benzylamine)porphyrin into
corresponding acryloyl monomers and benzylproxide as an initiator and dmf solvent was carried out
to investigate its catalytic activity in the oxidation reactions.
Keywords: porphyrin, polymer, acryloy chloride, oxidation
228
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P-391
Trends in the conversion of verdoheme to iron-biliverdin
a,b
b
Reza Latifi, Baharan Karamzadeh,b Nasser Safari,*a Mahin Gheidi,a and Sam P. de Visser*b
a
Chemistry Department, Shahid Beheshti University, Evin, Tehran 1983963113, Iran
Manchester Interdisciplinary Biocenter and School of Chemical Engineering and Analytical Science,
University of Manchester, 131 Princess Street, Manchester M1 7DN, United Kingdom
(emails: [email protected])
We focus in this work on the difference in reactivity between Fe(III)-superoxo verdoheme and
Fe(II)-superoxo verdoheme. Thus, we show that both mechanisms are stepwise with an initial C–O
bond activation to form a ring-structure where the verdoheme is distorted from planarity. This is
followed by a homolytic dioxygen bond breaking that directly leads to iron-oxo biliverdin products.
The Fe(III)-superoxo verdoheme mechanism proceeds via two-state-reactivity patterns on closelying singlet and triplet spin state surfaces, whereas the Fe(II)-superoxo verdoheme process shows
single-state-reactivity on a doublet spin state surface. In both the Fe(II)-superoxo verdoheme and
the Fe(III)-superoxo verdoheme the rate determining step is the C–O bond activation, with
substantially lower barriers on the Fe(II) surface of 14.2 kcal mol–1 in the gas phase compared to
27.1 kcal mol–1 for the low-spin Fe(III) process. The effect of a dielectric constant on the reaction
barriers was tested but shown to be small. These studies imply that most possibly the enzyme
reacts via an Fe(II)-superoxo verdoheme intermediate rather than Fe(III)-superoxo verdoheme.
Finally, we tested the effect of the axial ligand on the reaction mechanism. These studies show that
the axial ligand effect on the Fe(III)-superoxo verdoheme mechanism is small, whereas in the
Fe(II)-superoxo verdoheme mechanism it favours the natural ligand imidazole.
Keywords: Heme oxygenase, DFT, Verdoheme, Fe(III)- and Fe(II)-superoxo verdoheme.
P-392
Substrate hydroxylation by MnV=O porphyrin and MnIV=O porphyrin oxidants, what is
the best oxidant?
Reza Latifi, a,b Laleh Tahsini,b,c Baharan Karamzadeh, b Wonwoo Nam, *c and Sam P. de Visser *b
a
Chemistry Department, Shahid Beheshti University, Evin, Tehran 1983963113, Iran.
b
Manchester Interdisciplinary Biocentre and School of Chemical Engineering and Analytical Science,
University of Manchester, 131 Princess Street, Manchester, M1 7DN United Kingdom.
c
Department of Chemistry and Nano Science and Department of Bioinspired Science, Ewha
Womans University, Seoul 120–750, Korea.
In biomimetic studies the analogous manganese (V)-oxo and their one electron reduced form,
manganese(IV)-oxo, have been well studied. Manganese-oxo oxidants are important biomimetic
oxidants able to catalyze substrate hydroxylation reactions. In this work we report density
functional theory studies on the reaction of [Mn=O(Por)Cl]0,– with AcrH2. The studies show that
although both oxidants are capable of hydroxylating AcrH2, the 1[MnV=O(Por)Cl] species is a more
active oxidant. The reactions proceeds with a fast spin state crossing from the ground state singlet
to the triplet spin state prior to a hydride transfer. The work is fully consistent with previous studies
on iron-oxo porphyrins and manganese-oxo porphyrins and shows that the reaction proceeds via
two-state-reactivity on competing singlet and triplet spin state surfaces. Also to validate our findings
we did a series of benchmark studies on the reactant complexes and compared our results with
available spectroscopic data on MnV=O(TDCPP) with TDCPP = meso-tetrakis(2,6chlorophenyl)porphyrin.
Keywords: C–H abstraction, Mn-oxo, Porphyrin, DFT.
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229
P-393
The Study of Hydroxylation Reactions by Heme and Nonheme Iron- and manganeseOxo Oxidants
Reza Latifi, a Nasser Safari, a and Sam P. de Visser *b
Manchester Interdisciplinary Biocenter and School of Chemical Engineering and Analytical Science,
University of Manchester, 131 Princess Street, Manchester M1 7DN, United Kingdom
a
b
Mononuclear heme and nonheme iron containing systems are versatile and vital oxidants of
substrate hydroxylation reactions in many biosystems, whereby the rate constant of hydroxylation
correlates with the strength of the C-H bond that is broken in the process. High-valent iron(IV)-oxo
species have been identified as the active oxidant of several heme and nonheme enzymes, and
have been shown to be able to hydroxylate C-H bonds of substrates very efficiently. Research on
P450 enzymes is hampered due to the fact that the active oxidant of these enzymes is elusive,
although indirect evidence through kinetic isotope effect studies suggests that a high-valent
iron(IV)-oxo heme cation radical is the intermediate responsible for substrate monoxygenation. In
this work, to establish the fundamental factors that govern substrate hydroxylation by these
enzymes we have done a systematic density functional theory study on substrate hydroxylation by a
range of different iron-oxo oxidants and Mn-oxo complexes using heme and nonheme ligands. We
will show the effect of axial ligands and also the nature of central metal on the selectivity and the
mechanism of hydroxylation by Mn-oxo and Fe-oxo oxidants.
Keywords: Iron-oxo, Hydroxylation, DFT, Heme and nonheme oxidants.
P-394
Synthesis and Characterization of Anatase Nano-sized with Various Morphologies in
Different Conditions
Mohammad Hassan Loghmani, Abdollah Fallah Shojaie*
Department of Chemistry, Faculty of Science, University of Guilan, P.O.Box 1914, Rasht, Iran
Corresponding author E-mail: [email protected]
Anatase nano TiO2 powders were prepared by two different methods. One is the sol-microwave
method and the other is hydrothermal condition synthesis. The materials characterized by XRD,
Raman, SEM, TEM and FT-IR techniques. A microwave oven (800W) was used as the microwave
source. Under 2.45GHz microwave irradiation, titanium tetra-isopropoxide (TIP) was quickly
hydrolyzed and anatase was formed in a short time (<6 min). In addition, a simple sol to gel
conversion route has been followed for the preparation of anatase phase at 120 ◦C under
hydrothermal condition. TEM micrograph depicts that samples are vary in shape and size. The
shape of the microwave-assisted anatase, was observed as nanocrystal with average size of 30
nm is consistent with the XRD results. In the other hand, a mix of anatase nano rod and
quadrangular particles were formed under hydrothermal method. Note that these nano rods are 20
nm in length and 5 nm in width. XRD and Raman spectroscopy confirmed both microwave-assisted
and hydrothermal nano TiO2 have a high degree of crystallinity and existence of fully anatase phase.
Keywords: Microwave, Hydrothermal, Anatase, Nano rod
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P-395
Synthesis and characterization of phenanthroline complex of molybdenum (VI)
R. R. Khojasteh,* S. Lotfalian saremi, M. Ahmadzadeh
Department of chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran
The development of rutes and strategies for the design and preparation of complexes of 4d metals
in moderate oxidation states is of great importance in magnetochemistry, bioinorganie chemistry,
materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors,
especially phenanthroline, have been widely used to form complexes with interesting structural
motif. Reaction of Mco6 (M= Cr, Mo, W) with phenanthroline has been done in 1935 and produced
an interesting stereo structure, but the reaction of MoO2 (acac)2 {acac=acetylacetonato} with
phenanthroline has not been studied yet. So, in this refer first of all we prepared MoO2 (acac)2
and then mixed it with phenanthroline and we studied different aspects of this synthesis. The
structure of the product was examined by 1H ,13C-NMR, IR spectroscopy and elemental analysis.
The formation of the product [MoO2 (phen)2] – type is confirmed.
Keywords: dioxomolybdenum, phenanthroline, synthesis
P-396
Synthesis of Bridged Zirconocene Dichloride [Si(CH3)2(C5H4)2]ZrCl2
Behzad Lotfi, Ali Nemati Kharat*
([email protected])
Bis(cyclopentadienyl) group IV metal complexes are currently introduced in industry as a new
generation of Ziegler–Natta catalysts for the polymerization of olefins. The addition of a linkage
between the two Cp(cyclopentadienyl) rings has enabled the precise manipulation of the steric
environment encountered by reactive molecules such as α-olefins, and the development of
metallocenes for stereoregular olefin polymerization has proceeded from this advance. Increasing
the bridge length generally increases the centroid–metal–centroid (Cp-M-Cp) angle, which can
change polymerization characteristics. The CH2CH2 and Si(CH3)2 bridges, by far the most popular
bridging moieties, give rise to similar Cp-M-Cp angles, but the ethylene bridge allows a wide range
of relative motion between the two halves of the ligand which may lead to decreased molecular
weight and stereocontrol in olefin polymerization relative to the more rigid silylene-bridged
analogues. In this research we have prepared Si(CH3)2(C5H5)2 by adding of the
dichlorodimethylsilane to THF solution containing NaC5H5 at -60°C. The contents of the reaction
flask were then cooled to -80°C, and a solution of n-butyllithium in hexane was added slowly then a
THF solution containing ZrCl4 was added to the slurry of the dilithio salt. The product residue was
washed with small portions of cold pentane and then extracted and recrystallized with CH2Cl2 to
give pale yellow crystals.
Keywords: ansa-Zirconocene, Ziegler–Natta catalyst, polymerization
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P-397
TiO2 supported on kaolin: Enhancement in adsorption and photoactivity
M.Lotfi , M.A. Zanjanchi * , A.Mohammad khah
Department of Chemistry, Faculty of Science, University of Guilan , Rasht , Iran
Abstract: Titanium dioxide (TiO2) has received a great attention in the field of research and
development as a promising photocatalyst to promote the degradation of organic contaminants in
water. A novel titania impregnated kaolin (TiO2/K) photocatalyst was synthesized by a modified
two-step method. It consists of hydrolysis of titanium tetrachloride and heterocoagulation with pretreated kaolin clay. The TiO2/K photocatalysts were characterized using X-ray diffraction (XRD),
scanning electron microscopy (SEM), electron microprob analysis (EDX), IR spectroscopy and BET
surface area measurement (BET). The kaolin, as a support for the titania particles has a
delaminated sandwich silica structure. Microscopic examinations revealed that the TiO2 particles
were uniformly deposited on the kaolin external surface. The photocatalytic activity was evaluated
by the degradation of methylene blue in aqueous solution. The TiO2/K photocatalysts demonstrated
enhanced adsorption and photocatalytic ability for the removal of methylene blue. The TiO2/K
adsorbent and photocatalyst can be easily separated and recovered from the water treatment
systems.
Keywords: Kaolin; TiO2; Photocatalysis; Clays; Adsorbent; Degradation
P-398
Copper(II) Schiff base Complexes as Ligand in Tin Chemistry: The Thermodynamic
Studies of Adduct Formation Between Diorganotindichlorides and Cu(II) Complexes
Najmeh Lotfi, Zahra Asadi*, Mozaffar Asadi*
Chemistry Department, College of Sciences, Shiraz University, Shiraz, I.R. Iran
(e-mail: [email protected]; [email protected] )
Several studies have been done on the molecular interaction between acceptor-donor systems,
specially the molecular structure of transition metal Schiff base complexes as ligands for tin
chemistry. Previous studies in our group have been shown that transition metal Schiff base
complexes especially Ni(II), Cu(II), Co(II) salicylaldimines are effective neutral donor ligands for
tin(IV)halides and the adduct was formed with different structural possibilities. Thermodynamic of
adduct
formation
between
R2SnCl2
e.g.
dimethyltindichloride,
diphenyltindichloride
anddibutyltindichloride as acceptor and some copper(II) Schiff base complexes such as : [Cu(Me4Bzo2[14]tetraeneN4)], [Cu (Me4-4-CH3Bzo2[14]tetraeneN4)], [Cu(Me4-4-ClBzo2[14]tetraeneN4)] and
[Cu(Me2Ph2-Bzo2[14]tetraeneN4)],
[Cu(Me2Ph2-4-CH3Bzo2[14]tetraeneN4)],
[Cu(Me2Ph2-4ClBzo2[14]tetraeneN4)]
where
Me4-Bzo2[14]tetraeneN4)
=
(
5,7,12,14tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclo tetradecine) as donor, has been studied in
acetonitrile by means of UV-Vis spectrophotometric analysis. The formation constant values and the
thermodynamic free energies were measured for 1:2 adduct formation at various temperatures (T
= 283-313K); show the trend of the adduct formation of the copper complexes with a given tin
acceptor decrease as follow: [Cu(Me4-4-CH3Bzo2[14]tetraeneN4)] > [Cu(Me4-Bzo2[14]tetraeneN4)] >
[Cu(Me4-4-ClBzo2[14]tetraeneN4)] > [Cu(Me2Ph2-4-CH3Bzo2[14]tetraeneN4)] > [Cu(Me2Ph2Bzo2[14]tetraeneN4)] > [Cu(Me2Ph2-4-ClBzo2[14]tetraeneN4)]. The trend of the reaction of
diorganotin(IV)dichlorides toward a given copper Schiff base is as follow: Ph2SnCl2 > Me2SnCl2 >
Bu2SnCl2. Adducts have been synthesized and characterized by 1HNMR, 119SnNMR, IR, UV-vis
spectra and elemental microanalysis (C.H.N) methods.
Keywords: Donor-acceptor adducts, Diorganotin(IV)dichloride, Thermodynamic, Tetraaza Schiff
base, Copper(II)complexes.
232
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P-399
Crystal structure of heteronuclear oxo-centered acrylate complex
Nahid Lotfian*, Mohammad Yazdanbakhsh
Department of Chemistry, faculty of Science, Ferdowsi University of Mashhad, Iran
Trinuclear µ-oxo-centered carboxylate clusters have been extensively investigated in the last
decade, because of their biological and catalytic properties. In this work trinuclear complex [Fe2Cr
(µ3-O) (C3H3O2)6(H2O) 3] +NO3- has been synthesized and characterized by X-ray crystallography
from single-crystal data. This complex crystallize in the monoclinic system, space group P21/c, with
four molecules per unit cell. The unit cell dimensions are a = 12.547(6) Å, b = 15.602(7) Å, c =
16.052(7) Å, β= 90.345(11) °. In this structure the central Fe2Cr consist of a planer triangular
arrangement of metal ions. The three metal ions are bound to central oxygen atom and adjacent
metal ions are bridged by two carboxylate ligands. The monodentate ligands (H2O) complete the
octahedral coordination sphere.
Keywords: Crystal structures, Trinuclear complexes, Oxo-centered
P-400
Cationic metalloporphyrins in zeolite matrix as efficient catalysts for Monoterpenes
oxidation with H2O2/ammonium acetate
a
b
M. Madadia,*, R. Rahimib
Department of Chemistry, Iran University of Science & Technology, Tehran, Iran
The homogeneous and heterogenized metalloporphyrin complexes are active in the oxidation of
monoterpenes.
Under
homogeneous
conditions,
the
manganese(III)
tetra(4-Nbenzylpyridyl)porphyrin (MnTBzPyP) and Iron(III) tetra(4-N-benzylpyridyl)porphyrin (FeTBzPyP)
were impregnated (MnTBzPyP-NaYimp), (FeTBzPyP-NaYimp) in the NaY zeolite. These impregnated
complexes were prepared by impregnation of proportional amounts of metalloporphyrin complexes
on NaY and this was followed by evaporation of the solvent at room temperature. The new
materials were characterized by several techniques: chemical analysis and spectroscopic methods
(FT-IR, UV/vis, XRD, SEM, BET and 29Si MAS AMR). In this work the homogeneous and
heterogenized catalysts are used for efficient and selective monoterpenes oxidations and good
shape selectivity is observed. The selectivity of these heterogeneous catalysts does not change
appreciably even after three times of reusing, but their catalytic activity decreases marginally.
Analysis of the data indicates that the impregnated complexes exhibit different property from those
of the free complexes. The impregnated manganese(III) complex is catalytically very efficient as
compared to other Iron(III) complexes for the partial oxidation of Monoterpenes.
Keywords: Manganese(III)
Oxidation, Monoterpenes
porphyrin,
Heterogeneous
catalysts,
homogeneous
catalysts,
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P-401
Covalent Functionalization of Graphene Oxide By Aminoclay
Mahnaz Maddahfar, S. Jafar Hoseini*
[email protected]
Graphene oxide (GO) composed of planar, graphene-like aromatic domains of random sizes
interconnected by a network of cyclohexane-like units in chair configuration which are decorated by
hydroxy, epoxy, ether, diol, and ketone groups. While amino derivatives readily react with graphene
oxide, the exact nature of the chemical interaction between amine and graphene oxide is still under
debate in the literature. Burlinos et al. propose primarily covalent bonding via nucleophilic attack of
amines on epoxide groups. In contrast,Mastuo et al. suggest two interactions: hydrogen bonding
between amines and hydroxyl groups on the basal plane along with ionic binding of ammonium ions
to deprotonated hydroxyl groups. Herein, we have used an aminoclay, a phyllosilicate family of
molecular formula R8Si8Mg6O16(OH)4, where R = CH2CH2NH2 as the water dispersible support, and
its interaction with graphene oxide was investigated. Graphen oxide was prepared using modified
Hummers method and characterized by scanning electron microscopy, IR spectroscopy and x-ray
differaction. IR data showed that the main interaction between the amines and graphene oxide is
via ring-opening aminations of epoxides to yield 1,2-amino alcohols. The product showed high
solubility in water and can be used as an important surfactant (capping agent) for synthesis of
metal and metal oxide nanoparticles.
Keywords: Graphene Oxide, Aminoclay, Graphene
P-402
Synthesize and characterization of a new complex of organotin(IV) carboxylate
resulted from coumarin 3-carboxylic acid
a
V. Mahboobia,*, L.A. Sagathforoushb
Department of chemistry, Faculty of Science, Islamic Azad University,Arak, Iran
b
Payame Noor University (PNU), Khoy, Iran
Abstract: interaction between triphenyltin(IV) chloride with silver salt of coumarin 3-carboxylic acid
resulted new complex(fig.1)of organotin(IV) carboxylates.The new compound was confirmed by FTIR, 1HNMR and Mass spectroscopy. The results obtained from spectroscopic data proved that the
ligand bound to metal by it’s CO group. The complex will be tested for biological properties.
Keywords: organotin(IV) carboxylate, coumarin, biological activity.
234
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P-403
Production of 1-butene by the selective dimerization of ethylene over Ti
(OC4H9)4/THF/TEA with 1-bromo-2-chloroethane as a new promoter
a
M. Parvaria, S.M. Mahdaviania, D. Soudbar b, M. Parsa. c
Chemical Engineering Department, Iran University of Science and Technology (IUST), Tehran,
Iran
b
Research and Development Center, Arak Petrochemical Company, Arak, Iran
c
Department of Chemistry. Science Faculty, Islamic Azad University, Arak
[email protected]
The catalytic behavior of titanium tetrabutoxide (Ti (OC4H9)4) in ethylene dimerization was studied
in combination with triethylaluminum (TEA) co-catalyst, the cyclic ether of tetrahydrofuran (THF) as
modifier and 1-bromo-2-chloroethane as a new promoter. The experiments were performed at in a
1000ml stainless-steel pressure buchi reactor. The effect of changes in Al/Ti ratio and promoter/Ti
ratios has been investigated. The results showed that with addition of a vicinal halide compound (1bromo-2-chloroethane), the rate of ethylene consumption, conversion and selectivity to 1-butene
have been increased. The results are shortly. Some effective interaction modes of halogen group
with active Ti species in the catalytic cycle are proposed to explain the positive effect of halide in
ethylene dimerization reaction. As conclusion, the facile decomposition of dimeric TEA into
monomeric TEA can stabilize active center of Ti complexes and finally can lead to increase of
ethylene conversion and decrease of by-products (heavy and polymeric compounds).
Keywords: 1-butene, Ti (OC4H9)4, TEA, promoter, ethylene conversion
P-404
Synthesis and characterization of a number of Ln(III) Schiff base complexes containing
azo ligands
Mahsa Mahdavian, Reza Golbedaghi, Sadegh Salehzadeh*
Department of Chemistry, Bu-Ali Sina University, Hamedan, Iran
Azo compounds, with two phenyl rings separated by an azo (-N=N-) bonds, are versatile molecules
and have received much attention in research areas both fundamental and application [1-3]. We
have been interested in chemistry of tripodal Schiff base ligands [4]. In this paper at first, a new
series of symmetric salicylaldiminato Schiff base ligands were synthesized by reaction of tren and
tpt with 5-(4-X-phenyl)-azo-salicylaldehyde (X= H, Cl and CH3). Then a number of new Ln(III) (Ln=
La, Gd and Sm) of above ligands were synthesized and characterized by elemental analysis, IR, UVVis and mass spectroscopy in all cases and NMR in the case of ligands and Ln(III) complexes.
Keywords: Schiff base, azo ligands, tripodal ligands, Ln(III) complexes
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P-405
Synthesis and spectroscopic characterization of sandwich sitting-atop complexes of
meso-Tetraarylporphyrins and SeCl4
M. Mahloujifar, H.Dehghani*
Department of Inorganic chemistry Faculty of Chemistry, University of Kashan, Kashan, Iran
Porphyrins are a group of importance synthesis and natural compounds that have Many biological
applications. Porphyrins posses attractive optical, electronic and catalytic properties that are of
intrest in areas such as molecular sensors, photodynamic therapy and in the developing field of
molecular electronics, where potential applications include optical memories for data storage.
Sanwich-type complexes of porphyrins have aroused increasing interest during recent years.These
complexes have potential applications as prototype materials for visual displays, semiconductors
and gas sensors in pollution control. In this study, several substituted meso-tetraphenylporphyrins,
H2T(X)PP(x=H,4-CH3,4-OCH3,4-Cl,4-CH(CH3)2 ,3-CH3,3-OCH3) have been prepared. These free base
porphyrins interact with selenium (IV) chloride (SeCl4) in mild condition to form sandwich sittingatop complexes. 1H NMR,13C NMR, UV-Vis and FT-IR results showed that two lone electron pairs of
pyrrolenine nitrogens in the two porphyrin macrocycles act as σ-electron donors to empty orbitals
of central atoms in SeCl4 for formation of sandwich-type sitting-atop complexes [SeCl4(H2T(X)PP)2].
Key Words: sandwich-type complex, Porphyrin, Selenium(IV) chloride, Sitting-atop, SAT complex
P-406
Polymer-supported imidazolinum salysilaldehyde acetylacetonate ethylene diimine
molybdenyl Schiff base catalyst as effective, selective and highly reusable catalyst in
epoxidation of alkenes
a
Mina Majidia, Gholamhossein Grivania,*
In recent years much effort has been devoted to heterogenization of homogeneous catalysts on
insoluble supports because homogeneous catalysts suffer from drawback of poor catalyst recovery
and product separation. To overcome this shortcoming, homogeneous active catalysts have been
immobilized in several heterogeneous organic and inorganic supports. Thus here we report the
preparation of polymer-supported molybdenum-based catalyst as efficient heterogeneous Schiff
base catalyst. Choloromethylated polystyren was reacted with imidazole and by reaction of obtained
resin with choloromethyl salysilaldehyde polymer-bound imidazolinum salysilaldehyde were
prepared. Then it was reacted with ethylene diamine and polymer-supported imidazolinum schiff
base ligand with pendant amine group was prepared. In the subsequent reaction of this supported
ligand with MoO2(acac)2 polymer-supported molybdenyl schiff base catalyst was prepared that show
high activity, reusability and selectivity in epoxidation of various alkenes in the presence of TBHP.
Keywords: Polymer-support; Molybdenyl dication; Schiff base complex; Epoxidation.
236
IICC12
P-407
Synthesis and Characterization of Cystein Containing Metal Complexes and Metal
Sulfide nano structures (M= Cd and Hg)
E. Malakooti a, M Ranjbar b*, R. Nozaria, S. Sheshmania
Department of Chemistry, Islamic Azad University, Shahr-e Ray Branch, Tehran, Iran
b
Department of Chemical Industry, Iranian Research Organization for Science and Technology,
Tehran, Iran ma_randjbar@ yahoo.com
a
In recent years, the preparation of transition metal nano-structures, as important semiconductor
materials has attracted widely attention. In this study, preparation and characterization of nanostructured Hg(II) and Cd(II) complexes of cysteine from the reaction between cysteine ligand (2Amino-3-mercaptopropanoic acid), and Hg(CH3COO)2 with potassium iodide at room temperature
and ambient pressure in an ultrasonic vessel was investigated. Also the nano structures of CdS, HgS
and microstructure of HgI2 were prepared from nano structures Hg(II) and Cd(II) cysteine
complexes as precursor by hydrothermal decomposition and pyrolyses method. The nano structures
were characterized by elemental analysis, FTIR and UV-visible spectroscopy, X-ray powder
diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), nuclear
magnetic resonance (NMR) and energy– dispersive X-ray (EDX) techniques. The results showed
that the chemical formula for the complexes are: [MI2(C3H5NO2S)]n, M= Hg and Cd. Hg(II) complex
has dendrite shape nano structures while Cd(II) complex has hexagonal nano particles.
Keywords: Cysteine ligand, Nano structures, Mercury complex, Cadmium complex
P-408
Synthesis and characterization of 1,10-phenanthroline manganese (II) complexes of
phenylcyanamide ligands
a
Kh. Maleka, H. Chiniforoshana*,
Department of Chemistry, Isfahan University of Technology, Isfahan, Iran
([email protected])
The coordination chemistry of phenylcyanamide ligands is expected to be as potentially rich as that
of the pseudohalides (for example,azide or thiocyanate). The attachment of a phenyl ring to the
cyanamide group adds an extra dimension not present in azide or thiocyanate ligands. An extensive
π conjugation between the cyanamide group and phenyl ring provides an energitically favorable
means by which a metal ion can couple into a conjugated π organic πsystem. In this study, at the
first, phenylcyanamide and some its derivatives were readily prepared in high yields from the
corresponding anilines by desulfurization of the thiourea derivative.Then Mn(II) phenylcyanamide
was reacted to 1,10 –phenanthroline for the formation of a new complex Mn(II) phenylcyanamide
containing 1,10-phenanthroline closed rings.Diffrent propertise of this complex was compared with
an open ring Mn(II) phenylcyanamide tetra phenylporphyrin complex. Each of the complexes has
been characterized by IR, UV-Vis spectroscopies and crystallography.
Keywords: phenylecyanamide ligands, aniline,desulfurization, 1,10-phenanthroline, crystallography
IICC12
237
P-409
Sol–gel preparation of nano-structured zinc oxide thin films for photocatalytic
applications: solvent effect
Nasrin Talebian*, Najmieh Maleki
Department of Chemistry, Faculty of Science, Islamic Azad University, Shahreza branch, Iran
ZnO thin films were prepared by sol–gel method in various alcohols and deposited on glass
substrate using dip coating technique. The starting material was zinc acetate dihydrate, and
ethanol, isopropanol and 1,4- butandiol were used as solvent. The cetyltrimethyl ammonium
bromide (CTAB) was used as the modifier and monoethanolamine (MEA) as stabilizer. The effects of
reaction media on the product morphology as well as crystallization mechanism and optical property
were investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis
spectroscopy, respectively. Photodegradation of intra crown orange, an azo dye was used as a
model reaction to test the photocatalytic activity of the ZnO samples. The influence of the solvent
polarity on the morphology of ZnO samples and the effect of the morphologies on the
photocatalytic activity are discussed.
Keywords: zinc oxide; sol-gel method; photocatalytic activity; alcohol; azo dye.
P-410
Synthesis and Characterization of a copper(І) cluster containing CuI
-NCS-CoII: [PPh4]2[MoS4(CuNCS)3CoCl2]
Sh.Maleki* ٫ M.Esmhosseini
Department of Chemistry, University of Urmia, Urmia, Iran
Thiometalate anions [MS4]2, (M=Mo, W) can function as versatile multidentate chelates to combine
with Cu(I) ions leading to the molecular architecture of many heterometallic coordination polymers.
Many of these complexes showed potentially useful properties such as conductivity and non-linear
optical activity. All the reactions were carried out under the protection of dry oxygen-free dinitrogen
at room temperature. Solvents were dried with appropriate drying agents. [NH4]2MoS4 previously
was prepared as a beginning substance was dissolved in pph4Cl in H2O , and the subjected solution
to stirrer in order to remove NH3. Water was added to replace that lost due to evaporation, and the
reaction mixture filtered into i-PrOH. The precipitated product was isolated, washed with i-PrOH and
Et2O and dried in vacuum. Prepared (PPh4)2MoS4 reacted with CuCl in acetone to form
(PPh4)2MoS4(CuCl)3.[PPh4]2MoS4+CuCl [PPh4][MoS4(CuCl)3] then (PPh4)2MoS4(CuCl)3 and KSCN
were dissolved in acetone after the reaction mixture had been stirred for 30 min at room
temperature added to CoCl2 had been stirred for 5 hr, the deep green solution was filtered to
remove the precipitated KCl and the filtrate was evaporated by vacuum pump. The compound was
characterized by elemental analyses, IR spectra and UV–visible spectra. Cu(І) coordinate to Co(ІІ)
through bidentate –SCN- ligand.
Keywords: Synthesis ٫ Thiometalate ٫ Molybdan ٫ Cluster
238
IICC12
P-411
Synthesis and Crystal Structure of a Sn(IV) Complex
F. Manteghia,*, M. Ghadermazib, and H. Aghabozorgc
Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran
c
Department of Chemistry, Islamic Azad University, North Tehran Branch, Iran
a
b
Continuing the synthesis of (pipzH2)(pydc) metal complexes, a complex with the formula of
(pipzH2)[Sn2(pydc)4(OH)4-µ-(OH)2]·6H2O, where pydcH2 is pyridine-2,6-dicarboxylic acid and pipz is
piperazine, was prepared. The characterization was carried out using IR, 1H NMR, 13C NMR
spectroscopy, and single crystal X-ray diffraction. The structure has O–H...O and N–H...O hydrogen
bonds and ion-pairing as the main factors in formation of the extended structure. Further studies on
the compound will be done. As a result, the title compound has a binuclear and bridged structure
that is not very usual in the (pipzH2)(pydc) series.
Keywords: Tin, Pyridine-2,6-dicarboxylic Acid, Piperazine, Crystal Structure.
P-412
Synthesis and Crystal structure of a Nine-coordinated Cerium(IV) Complex with
Pyridine-2,6-dicarboxylic acid and Diethyltriamine
F. Manteghia,*, M. Ghadermazib, N. Kakaeib and S. Mehdizadehb
a
b
The complex (detaH3)2[Ce(pydc)3] · 6H2O or 3(C21H9CeN3O12),2(C4H16N3),16.75(H2O) was prepared
using a proton transfer compound (detaH3)2(pydc)3 and Ce(NO3)6(NH4)2 · 6H2O, where pydc is
pyridine-2,6-dicarboxylate and deta is diethyltriamine. The Ce(IV) ion is coordinated by six oxygen
and three nitrogen atoms of the (pydc)2– ligand. The triply protonated amine, detaH3 as
counterion, present in structure balances the charge of anionic complex. The complex has ionpairing interactions, O–H···O, N–H···O and C–H···O hydrogen bonds, π–π stacking as well as van
der Waals forces as the main factors in formation of their supramolecular structures. Similar to
many other Cerium compounds especially with (pydc)2−, the coordination number of nine is
observed.
Keywords: Pyridine-2,6-dicarboxylic acid; Diethyltriamine, Cerium(IV); X-ray diffraction; Crystal
structure
IICC12
239
P-413
A new mono- and ZnII –CuII complexes with asymmetry dinucleating macroacyclic
ligand containing double set donor's coordination sites (N4O2 and N2O2)
Interest in the investigation of new dinuclear complexes is still increasing. A number of such
complexes were reported earlier due to their potential relevance in bioinorganic chemistry, magneto
chemistry, redox Chemistry, coordination chemistry, homogeneous catalysis, isomerization of
dangle arms and remarkable rearrangements. In this work, we report the synthesis of ZnII- CuII
complex by stepwise method. At first, The precursor monometallic dialdehyde complex was
prepared and then the Zn(II)-Cu(II) complex was prepared by condensation of monometallic
complex with methyl amine and introduction of second metal, consecutively. The X-ray data
demonstrated that the dangle pyridyl arms disposed trans in both mono and bimetallic complexes.
On the other hand, the isomerization didn’t occur, and the geometry around the Cu(II) ion is square
planer. The prepared complexes were characterized by elemental analysis, spectroscopies
techniques, molar conductance measurements and X-ray crystallography.
Keywords: Dinucleating ligand, ZnII -CuII complex, asymmetry, Isomerization, macroacyclic ligand
P-414
Preparation and characterization of new ZnII –CuII heterobimetallic complex with
dicompartmental macrocyclic ligand: study of intramolecular cyclo-addition
Heterodinuclear metal complexes are of current interest for their physiochemical properties. The
devise of dinucleating ligands that incorporate dissimilar metal ions to form discrete heterodinuclear
complexes is of much importance in attempts to mimic the active sites of metalloenzymes and to
search appropriate systems for binding and activating simple molecules and in investigations
concerning the mutual influence of two metal centers on the electronic, magnetic and
electrochemical properties of such heterodinuclear systems. So far phenol-based macrocyclic
ligands having two dissimilar metal binding sites sharing two phenolic oxygen atoms have been
used for the study of di-µ-phenolato heterodinuclear metal complexes. In this work, we were
studied influence of the size of closed site link on the isomerization and the formation of the fivemembered imidazolidine ring in the diethylenetriamine link. The prepared complexes were
characterized by elemental analysis, spectroscopies techniques, molar conductance and X-ray
crystallography.
Keywords: Dicompartmental ligand, Heterobimetallic complex, Isomerization, macrocyclic ligand,
phenol based, Imidazolidine Ring
240
IICC12
P-415
Pentacoordinate Cobalt(III) Complexes with Unsymmetrical Tetradentate Schiff base
and Phosphine Ligand: Synthesis and Characterization
a
Y. Mardania, Sh. Esmaielzadehb*
b
[email protected]
Co(III) Schiff bases have been extensively studied because of their interesting properties. Cobalt
complexes besides existing in several stereochemical disposition, interact with molecular oxygen
ultimately oxidizing the complexes Co(II) to Co(III). The best known biological function of cobalt is
its involvement in the coenzymes related to vitamin B12. A new series of cobalt Schiff base
complexes containing the tetradentate ligand such as (cd5-ClsalMeen){methyl-2-{[1-methyl-2-(5chloro-2-phenolate)methylidynenitrilo]ethyl}aminato(-1)-1-cyclopentenedithiocarboxylate,
(cd5BrsalMeen) {methyl-2-{[1-methyl-2-(5-bromo-2-phenolate)methylidynenitrilo]ethyl}aminato(-1)-1cyclopentenedithiocarboxylate
and
(cd5-NO2salMeen)
{methyl-2-{[1-methyl-2-(5-nitro-2phenolate)methylidynenitri-lo]ethyl}aminato(-1)-1-cyclopentenedithiocar-boxylate
have
been
synthesized. Their have been characterized by UV-Vis, 1HNMR, IR and elemental analysis
techniques.
Keywords: Tetradentate ligand, Schiff base, Cobalt complexes, Coordination.
P-416
Synthesis and characterization of new Cu(II) phosphorus complexes
Sh. Masoudian and H. Hosseini Monfared*
Department of Chemistry, Zanjan University 45195-313, Zanjan, Iran
Phosphorous compounds are one of the most important branches in heteroatomes in organic and
bioorganic chemistry. These compounds are widely used in organic synthesis and extensive
researches have been done to investigate reactions between phosphorous and other active
reagents. Organophosphorous compounds, those bearing a carbon atom bound directly to a
phosphorous atom, are synthetic targets of interest, at least because of their value for a variety of
industrial, biological, pharmacological and chemical synthetic uses. As a result, a large number of
methods have appeared describing novel synthesis of organophosphorous compounds. In this study
we report a simple and environmentally benign methodology for the synthesis of two new ligands
from phosphorous. The synthesized compounds were characterized by 1H, 13C, 31P NMR and IR
spectroscopy and elemental analyses. In the preparation of the ligands, phosphoric acid, N-methyl
aniline and aldehydes reacted in the presence of an acid to give [(methyl-phenyl-amino)methyl]
phosphonic acid (1) and [(methyl-phenyl-amino)phenyl-methyl] phosphonic acid (2). The cupper(II)
complexes of the ligands were synthesized and characterized by 1H NMR and 13C NMR spectroscopy.
High yield, mild reaction condition and easy workup are of the advantages of this procedure.
Keywords: Phosphorus compound, Heteroatom, Organophosphorous, Phosphonic acid.
IICC12
241
P-417
Convenient preparation and characterization of some new Sciff base ligands and their
complexex with metal (II) ions
Sh. Masoudian*, H. Yahyaei,
Department of Chemistry, Islamic Azad University 49195-467, Zanjan, Iran
The development of the so-called Schiff base compounds has attracted a lot of interest in the fields
of coordination chemistry and material sciences. Transition metal complexs with oxygen and
nitrogen donor Schiff bases are of particular interest, because of their ability to posses unusual
confoguration, be structurally labile and their sensitivity to molecular environments. These
compounds also find many important catalytic applications, ranging from asymetric epoxidation to
various types of polymerization as well as their application for preparation of ion selective electrods.
In this paper, we have been studied the preparation of complexes of these Schiff bases with
transition metal ions under mild conditions. The corresponding complexes were characterized by 1H
NMR, 13C NMR, IR spectroscopies and elemental analysis (CHN). These complexes was synthesized
with High yield.
Keywords: Schiff base, Coordination Chemistry, Complex, Transition Metal
P-418
Mononuclear [Pb(SalDMPDA)] complex with H2SalDMPDA: Synthesis and spectral
studies H2SalDMPDA (=2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-diyl)bis(azan-1-yl-1ylidene)bis(methan-1-yl-1-ylidene)diphenol)
Sh. Masoudian* and H. Hosseini Monfared
Department of Chemistry, Zanjan University 45195-313, Zanjan, Iran
Organometallic complexes containing Schiff bases have played an important role in coordination
chemistry of transition metals, mainly due to their stability, ease of preparation, structural variability
and variety of applications. Ligands with N and O donar atoms are important since their metal
complexes find widespread applications as homogeneous and heterogenous catalysts in various
organic transformation reactions. Furthermore, tetradentate Schiff base complexes are increasingly
important for designing metal complexes related to synthetic and natural oxygen carriers. In this
study, we report on the synthesis of a new Schiff base ligand (1) and its complex of Lead (II). By
the way, the confirmation of structure of this compound is proved by 1H NMR, 13C NMR and IR
spectroscopies and elemental analysis (CHN).
Keywords: Organometallic Complex, Schiff Base,Transition Metal, Lead(II).
242
IICC12
P-419
Efficient, rapid synthesis and characterization some schiff base ligands and their
complexes of oxovanadium (IV)
Sh. Masoudian* and H. H. Yahyaei
Department of Chemistry, Islamic Azad University 49195-467, Zanjan, Iran
Vanadium is a bio-essential element found in remarkably high concentration in marine ascidians,
certain mushrooms and polychaete worms. The coordination chemistry of vanadium has been
received increasing interest in the past few years due to its insulin-mimetic behavior and as a
constituent of the cofactors in vanadate-dependent haloperoxidases and vanadium nitrogenase. The
most important oxidation states of vanadium are +3, +4, and +5. And the V(IV) compounds are
the most commonly observed in the form of compounds of the vanadyl ion, VO2+. In this study we
report the preparation of some new Schiff base ligands and their complexes of oxovanadium (IV).
The corresponding complexes were characterized by 1H NMR, 13C NMR, IR spectroscopies and
elemental analysis (CHN). High yield and mild reaction condition are of the advantages of this
procedure
Keywords: Vanadium, Coordination Chemistry, Complex, Oxidation
P-420
A Green Synthesis Technique for Functionalization of Carbon Nanotubes with Magnetic
Nanoparticles
Hassan Masrouri, Farnaz Movahedi and M.Z. Kassaee*
Carbon nanotubes (CNTs) have unique electrical and mechanical properties combined with chemical
stability which makes them potential candidates to serve as building blocks for several device
architectures in chemical sensors, hydrogen energy storage, catalyst support, electronic devices,
etc. Chemical modification and construction of complex new structures from carbon nanotubes will
allow a much broader applicability of these materials with tailor-made properties. Functionalizing
CNTs with magnetic nanoparticles can combine the features of magnetic nanoparticles and CNTs,
which may result in novel chemical and physical properties, and thus promising applications. The
main purposes of this work are to present a facile, a general, and an effective approach to magnetic
multiwall carbon nanotubes based on the convex surfaces of MWCNTs. Initially, Naked Fe3O4
nanoparticles were prepared by chemical coprecipitation method and were functionalized with 3aminopropyltriethyloxysilane (APTES). On the other hand, MWCNTs were functionalized with HNO3
and then SOCl2. Ultimately, magnetic nanoparticles were anchored to the surface of MWCNTs
through the formation of amide bonds. All of the steps in construction the ultimate catalyst are
verified with characterization analysis such as XRD, FT-IR, ICP, TGA, SEM and TEM.
Keywords: Fe3O4 nanoparticles, Multiwall carbon nanotube, Functionalization, Amide bonds
IICC12
243
P-421
Silica-supported ethylenediimine bis (acetylacetonato) dioxomolybdenum as
epoxidation catalyst
a
Sara matinia, Gholamhossein Grivani*,a
Heterogenization of homogeneous catalysts, presents a rapidly expanding research area providing
advantages such as easy handling and product separation, and catalyst recovery. A wide variety of
heterogenized catalysts are the metal complexes anchored on silica support. Many of them have
been developed by chemically modified silica gels with organic functionalities. Here we describe the
immobilization of ethylenediimine bis (acetylacetonato) dioxomolybdenum on cabosile as silica
support and investigate the catalytic activity and reusability of supported catalyst in epoxidation of
alkenes. Cabosil was functionalized with actylacetone and in subsequent reaction with ethylene
diamine resulted in silica-supported ethyleneimine-amine acetylacetone. By reaction of this
functionalized silica with MoO2(acac)2 in
DMF the silica-supported
ethylenediimine bis
(acetylacetonato) dioxomolybdenum (a) was produced. This catalyst show high activity and
selectivity in epoxidation of different alkenes in the presence of TBHP.
Keywords: Silica-support; Molybdenyl dication; Schiff base complex; Epoxidation.
P-422
Catalytic activities of heteropoly acid/porous hybrid materials in the synthesis of
perimidines
N. Mahdinbabayi, M. Zendehdel*, A. Mobinikhaledi
Department of chemistry, university of Arak,Arak,Iran
A series of hybrid heteropoly acids (HPA) has been prepared. The HPA/NaY and HPA/NaY/MCM-41
hybrids of the synthesized catalysts were characterized using XRD, BET, TGA, SEM and FT-IR
techniques. The results show that reasonable amount of HPA in HPA/NaY and HPA/NaY/MCM-41
hybrids remains even after washing with water, which indicates that heteropoly anions were
strongly bonded to the porous materials. The catalytic properties of the hybrid catalysts were
examined for the preparation of 2-(4-nitrophenyl)-2,3-dihydro-1H-perimidine. The catalytic activity
of different catalysts was in order of HPA/NaY>HPA/NaY/MCM-41>NaY>HPA>MCM-41.
Keywords: Heteropoly acids, HPA/NaY, HPA/NaY/MCM-41, Perimidine
244
IICC12
P-423
A Ni(II) and a proton transfer compound including pyridine-2,6-dicarboxylate and
phenylhydrazinium ions: synthesis, characterization and crystal structure
a
S. Mehdizadeha , M. Ghadermazia, F. Manteghib,* and N. Kakaeia
b
The new compounds, (phhyH)2(pydc), 1 and (phhyH)[Ni(pydc)(pydcH)]·3H2O, 2 phhy:
phenylhydrazine pydcH2: pyridine-2,6-dicarboxylic acid, were synthesized and characterized by IR,
1
H NMR, 13C NMR and UV spectroscopies, the structure of 2 was determined by X-ray
crystallography. In the crystal structure, the metal ion is six coordinated by two tridentate (pydc)2
and (pydcH) groups and each anionic complex unit, [Ni(pydc)(pydcH)] is accompanied by one
(phhyH)+ as counter ion and two water molecules. In compound 2, a large number of O–H···O, N–
H···O and C–H···O hydrogen bonds are observed. These interactions as well as other noncovalent
interactions such as ion pairing, C–O···π and π–π stacking play an important role in the formation
and stabilization of the crystal lattice. It can be concluded that both fragments of the ion pair is
involved in the synthesis of metallic compound providing a lattice of intermolecular interactions.
Keywords: Pyridine-2,6-dicarboxylic acid; Phenylhydrazine; Nickel; Proton transfer; Crystal
structure.
P-424
Investigation of carbonyl insertion reactions into M-Cp bond
Alireza Ariafarda,b,Tahmineh Mehrabia*, Zeinab Ejehia,Azadeh Moradzadeha,Reza Fazaelic
Gharb, Tehran, Iran ([email protected])
b
c
Tehran, Iran
a
Carbonyl insertion into an M-R bond is a primary step in the mechanism of many reactions
catalyzed by organometallic complexes. To this end, numerous theoretical and experimental studies
have been directed toward understanding the mechanism of such reactions. Recently, Hughes and
his co-workers for the first time studied the reaction of carbonyl insertion into Pt-Cp* where Cp* is a
η1 bound pentamethylcyclopentadienyl ligand. They showed that if two equivalents of PMe3
react with [(Cp*(Pt)(CO)I] complex, the product trans-[(Cp*CO)(Pt)(PMe3)2I] is formed. To
further understand the reaction mechanism and how the nature of the ancillary ligands positioned
cis /trans to the CO ligand affect the mechanism of the reaction, we studied the insertion reaction
using the model cationic complexes [(Pt)(Cp)(CO)(L)(L΄)]+ (L,L΄=PH3, PMe3, PCl3). Based on
the calculations we found two reaction pathways for the insertion reactions. For all the cases
studied, the direction that passes through a four-center transition state is the most favorable.
Considering that the electron donating ability of phosphines changes in the order
PMe3>PH3>PCl3, the calculations showed that the strong electron donor ligands positioned cis
to CO decrease the activation barrier while those positioned trans to CO increase the barrier.
IICC12
245
P-425
Investigation of ethylene polymerization and bicyclic formation by
betadiketiminate complexes
Alireza Ariafarda,b,Tahmineh Mehrabia*, Zeinab Ejehia,Azadeh Moradzadeha
Gharb, Tehran, Iran ([email protected])
b
c
Tehran, Iran
a
In the present study, the DFT calculations were used to investigate ethylene polymerization and
cycloadditon reactions promoted by betadiketiminate complexes with the general formula
[(CH(CHNPh)2M(CH3)]+ (M = Al, Ga, In, Sc, Y, La). The proposed mechanism for ethylene
polymerization and bicyclic formation by betadiketiminate complexes has been shown below. The
results show that the transition metal cationic complexes M = Sc, Y, and La can undergo easily
the ethylene insertion reactions with a relatively low activation barrier, implying that these
transition metal complexes are able to polymerize ethylene. However, the formation of the
bicyclic complexes on this species is found to be impossible from the thermodynamic point of view.
In contrast, the ethylene insertion into the M-Me bond where M = main group metal has been
shown
to
be
a
difficult
process.
This
suggests
that
these
complexes have much less ability to undergo the ethylene polymerization. Instead, they are reactive
toward the formation of bicyclic complexes. Our calculations predict that the size of the main group
metals has no effect on the energetic of the bicyclic formation reactions. In a given group, as the
metal center becomes heavier, the energy barrier to the insertion reaction increases.
Keywords: Density Functional Theory (DFT), Polymerization, cycloaddition reaction.
P-426
Synthesis and Characterization of Fe2O3 Nanoparticles from Initial one-dimensional
Fe(II) Coordination Polymer by Direct Thermolysis
a
A. Mehrania, A. Morsalia,*
Metal coordination polymers have been studied widely as they represent an important interface
between synthetic chemistry and materials science, with specific structures, properties (molecular
wires, electrical conductors, molecular magnets, in host-guest chemistry and in catalysis) and
reactivities. However the use of supramolecular complexes as precursors for the preparatation of
inorganic nanomaterials has not yet been investigated thoroughly. This article focuses on the
preparation and description of nano Fe(II) coordination polymer of [Fe(pyterpy)](SCN)2(MeOH) and
its conversion to nanoparticles of Fe2O3 by thermolyses in oleic acid at 286°C under air atmosphere.
Fe2O3 is an inorganic crystalline material with many applications. Metal oxides display appealing
electronic, optical, thermo electronic and photo electronic properties. Oleic acid as a surfactant
could prevent aggregating of Fe2O3 nanoparticles during the decomposition of Fe (II) coordination
polymer that can be lead to best morphology and size.
Keywords: Fe(II) Oxide, 4'-(4-Pyridyl)-2,2' : 6',2''-terpyridine, Nanoparticle, coordination polymer,
surfactant
246
IICC12
P-427
Synthesis, Crystal Structure and DNA Interaction of Zinc Complexes with 2,2'Dimethyl-4,4'-bithiazole
a
Z. Mehria, A. Abedia,*, M. Bordbareb and A. Tajarrodic
b
Department of Chemistry, Islamic Azad University, qom, Iran
c
Department of chemistry, University of science & technology, Tehran, Iran
Bithiazole is a part of Bleomycins (BLMs) antibiotics, widely used drugs that involves in DNA
cleavage. In the present work, synthesis of bithiazole complexes with zinc salts was considered.
[Zn(dm4bt)Br2] and [Zn(dm4bt)I2] complexes
(dm4bt is 2,2'-dimethyl-4,4'-bithiazole) were
prepared from the reaction of ZnBr2 and ZnI2 with dm4bt ligand in methanol. Both complexes were
characterized by elemental analysis, IR, UV-Vis, 1H NMR, and 13C NMR spectroscopy and their
structures were studied by single-crystal diffraction method. The biological activity of the complexes
has been evaluated by examining their ability to bind to calf-thymus DNA (CT DNA) by CD and with
UV-Vis. spectroscopy. The studies have shown that they can bind to CT DNA and the DNA-binding
constants have been calculated.
Keywords: Zinc complexes, Crystal structure, DNA Interaction, UV-Vis Spectroscopy, CD study.
P-428
Photocatalytic degradation of 2-mercapto pyrimidine over SnO2-ZnO nanostructure
multilayered thin films
Nasrin Talebian*, Parisa Memarnezhad
Iran ([email protected])
Multilayered thin film of ZnO/SnO2/ZnO/SnO2/ZnO has been deposited by Sol–Gel Dip-Coating
(SGDC) technique. The multilayered films were crystallized at 550 oC. Five stacked layers film is
examined for photodegradation of 2-mercapto pyrimidine as a model of organic pollutant under UV
light irradiation. The paper focuses on the structure characterization of multilayered deposits using
scanning electron microscopy (SEM) and X-ray diffractometer (XRD) method and on the
photocatalytic process. The analysis reveals structural inhomogeneities and different crystallite
growth processes as a function of number of deposited layers. The influences of operating
parameters on 2-mercapto pyrimidine degradation including initial concentration of 2-mercapto
pyrimidine and pH value of solution were examined. It was found that the photocatalytic
degradation of 2-mercapto pyrimidine on the Multilayer films followed pseudo-first order kinetics.
Keywords: Multilayered thin film, photocatalytic degradation, organic pollutant
IICC12
247
P-429
Synthesis and characterization of two new asymmetric tetradentate Schiff base
complexes derived from Methyl-2-{N-(2'-aminoethane}-amino-1-cyclopentenedithiocarboxylate with 3,5-di-tert-butyl salicylaldehyde
S. Menatia,*, A. Kakanejadib, , A. Taebc
Department of Chemistry, Islamic Azad University, Khorramabad Branch, Lorestan,Iran
b
Department of Chemistry, University of Lorestan, Lorestan, Iran
Department of Chemical Engineering,Iran University of Science and Technology, Tehran, Iran
a
c
Schiff bases are considered as a very important class of organic compounds which have wide
applications in many biological aspects. Schiff base-transition metal complexes are one of the most
adaptable and thoroughly studied systems. One New tetradentate ligand with NN'OS coordination
spheres was prepared and then the corresponding nickel (II) and copper (II) complexes were
synthesized. The ligand and the complexes were characterized by
elemental analyses,
IR,1HNMR,13CNMR, UV-vis and thermal analyses (TGA).The structure of copper{methyl-2-{N-[2(3,5-di-tert-butyl-2'-hydroxyphenyl)methylidynenitrilo]ethyl}amino-1-cyclopentedithiocarboxylate
has been determined by X-ray crystallography. The X-ray results confirm that the geometry of the
complex is slightly distorted square-planar structure. The copper (II) ion coordinates to two
nitrogen atoms from the imine moiety of the ligand, a sulfur atom from the methyl
dithiocarboxylate moiety and a phenolic oxygen atom.
Keywords: Schiff base complexes; X-ray crystal structures; Asymmetric complexes; Copper(II)
complexes; Nickel(II) complexes.
P-430
Preparation and characterization of Ecandrewsite ZnTiO3 nanopowder via sol–gel
process
M. Mikhak*, M.H. Habibi
Department of Chemistry, University of Isfahan, Isfahan, P. O. Box 81746-73441, Iran
TiO2 is one of the most extensively studied oxides because of its remarkable optical and electronic
properties. Because of strong confinement, the electrical and optical properties of nanocrystalline
TiO2 thin films vary significantly with grain size, and this ability to tune their physical properties
makes them an important candidate for potential application as photoelectronic materials. The
electron flow through semiconducting TiO2 thin films occurs via a hopping mechanism, which
exhibits a slow nonexponential current and charge recombination, thus limiting efficient charge
transfer. ZnO is also an important semiconductor and has been investigated widely for its catalytic,
electrical, optical, and photochemical properties and for application in blue/ ultraviolet (UV)
optoelectronic devices and in piezoelectric devices. In recent years, there has been growing interest
in iron titanium oxide and nickel titanium oxide thin films as good candidates for new optical fibers,
and as a sensor material for the detection of NO2 gas sensing applications. Furthermore, like the
other titanium-based systems, ZnTiO3 have a lot of potential for applications in non-linear optics. In
order to replace other materials, pure and high quality structures are needed. In the present
investigation, for the first time preparation and characterization of Ecandrewsite ZnTiO3 nanopowder
is reported by sol–gel process using a novel and stable single sol.
Keywords: Sol–gel process, Nanowires, Ecandrewsite.
248
IICC12
P-431
Crystal Engineering, Synthesis and Characterization of Polymeric Mercury (II)
Complexes Containing Carboxamide Ligands with Hydrogen Bonding
B. Mir Mohammad Sadegh, A. Aghabali, M. Mehdizadeh and H. R. Khavasi*
([email protected])
The development of crystal engineering in the last decade is resultant of understanding
intermolecular interactions in the context of packing, and utilization of this understanding in the
design of new compounds with predictable structural properties. The extended coordination
framework with desired structural features extremely depends on the nature of the organic ligands
(spacers) and metal ions (nodes). In this regards, we prepared N-(2-Pyridylmethyl)-2pyrazinecarboxamide (scheme), that contain pyridyl and carbonyl groups together. The
simultaneous presence of the N-donor and the carbonyl group (dual functionality) imparts these
ligands with special networking abilities. The dual functionality enables these ligands to be used for
the formation of stable metal-containing building blocks. We report here the synthesis of three new
compounds of mercury halides with this ligand which characterized by spectroscopic methods as
well as single crystal X-ray diffraction. The results show that in the complex (1), C-H…O and CH…Cl intermolecular hydrogen bonds, in the complex (2), weak interaction between the amide’s
hydrogen and one of the pyridine carbons in adjacent molecule with C-H…O and C-H…Br hydrogen
bonds and in the complex (3), N-H…C, similar to bromide complex , and C-H I hydrogen bonding,
lead to formation of the polymeric form of these complexes.
P-432
Syntheses, characterizations, and molecular structures of Ferric and Chromic
coordination compound consisting up dipicolinic acid and 2-aminopyridine
a
M. Mirzaeia,*, H. Eshtiagh-Hosseinia, H. Aghabozorgb
b
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Hydrogen bonding has emerged to be the most powerful tool among the directional intermolecular
interactions in supramolecular synthesis. Evolution of an assembly depends on the nature of the
functional group under consideration. To this end, assemblies involving the carboxylic group (COOH) are very widely applied because of its ability to form robust hydrogen bonds on its own and
also with the different compound and also mimics biological events. In this work, reaction of
pyridine-2,6-dicarboxylic acid (pydcH2) and 2-amino pyridine (apy) with chloride ferric and chromice
resulted in the formation two new supramolecularly coordination compounds, (apy) [M(pydc)2]
.pydcH2.5H2O; M = Cr and Fe. The title compounds were characterized with elemental analyses, IR
spectroscopy, TGA, potentiometric studies, and single crystal X-ray diffraction.
Keywords: Ferric, Chromic, Dipicolinic acid, 2-Aminopyridine, Hydrogen bonding, Single crystal Xray diffraction.
IICC12
249
P-433
Synthesis of nano Cadmium oxides via polymer route
H. Mirzazadeh*, M. lashanizadegan
Department of chemistry, University of alzahra, Tehran, Iran
Some of the transition metal oxides are used as semiconductors. The physical and chemical roperty
of these semiconductors are found to be size depend. Large scale synthesis of semiconductor nano
particles such as solid powder is important for industrial applications in the area of catalysis, photo
catalysis and micro electronics. In this work we present a simple method to produce nano CdO by
decomposition [Cd (OH)n] ⁿ− in aqueous solution. Then we use furnace to approach nano metal
oxide. For the synthesis of the CdO the reagents were of analytical grade and were used without
any further Purification. NaOH pellets were mixed with cadmium salt then the solution added to the
different amount of polymer. And stirred until a white precipitate appear then we use furnace for
produce cadmium oxide. This procedure shows us using polymer chain to grow 1D nano structures.
the effect of temperature, reaction time, dosage and molecular weight of polymer on the
morphology of metal oxides was investigated in detail. The products were characterized by X-ray
diffraction (XRD), scanning electron microscopy (SEM), FTIR and optical absorption measurement.
Variety of techniques are used to carry out structural characterization of the nano particles. It is one
of the easy, effective, fast and low cost ways for synthesis CdO which avoid the complicated
synthetic routes. And a new way for producing other metal oxides.
Keywords: CdO, Polymer, nano structure, synthesis.
P-434
Spectral characterization of novel teridentate (NO2) tin complexes containing Schiff
base ligands derived from 2,5-Dihydroxyaceto phenon and 2,4-Dihydroxyaceto phenon
with 2-amino phenol
a
M. Moalemian a,*, A.H. Kianfar b
Department of Chemistry, Islamic Azad University, Gachsaran Branch, ([email protected])
b
Department of Chemistry, Yasouj University, Yasouj, ([email protected])
Organometallic compounds containing lead, tin, and mercury are all commercially significant. A
large number of organotin compounds, for example, are used as pharmaceuticals, pesticides,
stabilizers, fire retardants, miticides, molluscicides, marine antifouling paints, surface disinfectants
and wood preservatives. Organotins with three organic groups can be powerful fungicides and
bactericides, depending on the organic group. Tin has a large number of organometallic derivatives
that are used commercially. Very little work has been carried out on the formation of tin complexes.
Therefore, in this study neutral tridentate NO2 type complexes of Sn have been synthesised using
Schiff base ligads formed by the condensation of 2-amino phenol in a molar ratio 1:1 with 2,5Dihydroxyaceto phenon and 2,4-Dihydroxyaceto phenon in alcohol medium. Structure of the ligands
and complexes were characterized on the basis of their micro analytical data, elemental analysis,
melting points, IR,1H NMR and UV–Vis spectra. The infrared spectrum of the complexes under
investigation confirmed the site of chelation, hence, the complexes showed strong absorptions due
to ν(C=N) and ν(C—O). The above absorptions have been shifted on complexation confirming the
chelation positions. Also, the band at 2900 cm–1 assinged to buthyl groups in the complexes.
Keywords: Tin complexes; 2,5-Dihydroxyaceto phenon; 2,4-Dihydroxyaceto phenon; 2-amino
phenol.
250
IICC12
P-435
Cu(II) Complex of Tridentate Carboxamide Ligand (Hqcq): Synthesis, Characterization
and Crystal structure of Cu(qcq)(CH3COO)(H2O)
S. B. Hoda Moeinsadata, Soraia Meghdadia, Mehdi Amirnasr*a, Kurt Mereiterb
a
b
Faculty of Chemistry, Vienna University of Technology, Getreidemarkt 9/164SC, Vienna, Austria
The binding of metal ions by proteins and peptides is of fundamental interest due to the importance
of metal ions in biological systems. The carboxamide [–C(O)NH–] group, ubiquitous throughout
nature in the primary structure of proteins, is an important ligand construction unit for coordination
chemists. As part of ongoing studies on carboxamides ligands, a highly efficient approach for the
synthesis of Hqcq = 8-(2-Quinolinecarboxamido)quinoline, using an environmentally benign reaction
medium has been developed. Cu(II) complex of the ligand (qcq⎯) has been synthesized and
characterized by elemental analyses, IR and UV-Vis spectroscopy and X-ray crystallography. The
crystal structure of [Cu(qcq)(H2O)(OAc)] where (OAc) is acetate ion, has been determined by X-ray
crystallography. The environment surrounding Cu ion is distorted octahedral (Fig. 1) with P2(1)/n
symmetry.
Keywords: Cooper(ll), Carboxamide Complex , X-ray crystal structure.
P-436
Preparation of hybrid hetropolyoxometalate, (bmim)5[W12CoO40].xH2O, and
investigation of its catalytic activity in synthesis of dihydropyrimidinones
A. J. Moghadam, V. Mirkhani*, S. Tangestaninejad, M. Moghadam, A. R. Khosrupoor, I.
Mohamadpoor-Baltork
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan, Iran
Polyoxometalates (POMs) are a subset of metal oxides formed primarily by Mo, W and the Group V
transition metals that represent a diverse range of molecular clusters with an almost unmatched
range of physical properties and the ability to form dynamic structures and acting as a set of
transferable building blocks that can be reliably utilized in the formation of new materials.
Recently, the interest in synthesis of dihydropyrimidinones is increasing tremendously because of
their therapeutic and pharmacological properties and also because of interesting biological
activities. However, some of the reported methods for the preparation of these heterocycles suffer
from disadvantages such as long reaction times, low yields and tedious work-up. A novel organic –
inorganic hybrid (bmim)5 [W12CoO40].xH2O (bmim:1- buthyl,3- methyl imidazolium) has been
prepared, a as green, reusable, efficient and heterogeneous hybrid catalyst in the synthesis of
dihydropyrimidinones and their derivatives by the reaction of aldehyde, urea and, β-ketoester
under solvent-free conditions. The corresponding DHPMs were obtaine in good to excellent yield.
the catalyst was reused several tims without long of its catalytic activity.
Keywords: Polyoxometalate, Ionic liquid, Organic-inorganic Hybrid compound
IICC12
251
P-437
Synthesis of some Mn(III) - 2-(2',4'-dihydroxyphenyl)-2-oxazoline Complexes and their
Application as Catalysts in Sulfides Oxidations
P. T. Moghadama,*, M. Bagherzadeha,
a
The oxazoline complexes (metal = Mn, Cr, Fe, Ru, Co, V and Ti) find widespread use as efficient
catalysts for the selective oxygenation of sulfides which can be of interest in the pharmaceutical
industry. Therefore two new manganese (III) complexes of 4-OHphox (2-(2',4'-dihydroxyphenyl)-2oxazoline) including [Mn(4-OHphox)3] and [Mn(4-OHphox)2(CH3OH)2]ClO4 have been synthesized.
4-OHphox characterized by IR, 1HNMR, 13CNMR and its complexes characterized by IR and
elemental analyses (CHN). These complexes can catalyze selective oxidation of various sulfides to
their corresponding sulfoxide with urea hydrogen peroxide (UHP) in mixture of CH2Cl2/CH3OH (1:3)
under ambient conditions. Their catalytic efficiency is strongly affected by the presence of a base,
such as imidazole and [Mn(4-OHphox)2(CH3OH)2]ClO4 complex is less effective catalysts than
[Mn(4-OHphox)3]. These complexes exhibit high catalytic activity in the oxidation reactions (100%
for methylphenyl sulfide) in short reaction times (5 min).
Keywords: Catalytic oxidation, Manganes, Oxazoline, Sulfide, Urea-Hydrogen Peroxide (UHP).
P-438
Synthesis, spectral identification of some bidentate Schiff base complexes of Co(II),
Ni(II), Cu(II)
E. Mahmoudabadi 1 , M. Montazerozohori 2 *,S. Joohari
2
Department of Chemistry, Yasouj University, Yasouj 75918-74831, P. O. Box353, Iran.
3
Department of Chemistry, Islamic Azad University, Yasouj Branch , Yasouj, Iran .
1
Schiff base complexes are known as important stereo-chemical models in main group and d-block
metal coordination chemistry because of their well accessibility and structural variety. They have
occupied a key role in the development of coordination chemistry as seen from an enormous
number of reports on Schiff base complexes, ranging from pure synthesis to modern
physicochemical and biochemically relevant studies of metal complexes. Recent interest in the
design, synthesis and characterization of symmetrical Schiff base complexes with d- block element
derived from the realization that the coordinated ligands around the central metal ions in natural
systems. Schiff base ligands and their metal complexes have different applications in fields such as
bioinorganic chemistry, material science, catalysis, separation and encapsulation processes. The aim
of the present study is to synthesize and identification of a new bidentate ligand of bis(3-phenyl
propanaldehydene)-1,2-benzenediamineand some its Co(II), Ni(II), Cu(II) complexes. These
complexes were synthesized whit slowly addition of the ligand to metal salt in ethanol with severe
stirring for 3-4h under reflux. The ligand and complexes were characterized by elemental analysis,
conductivity measurements, magnetic succeptibility, FT/IR and UV-Vis spectra.
Keywords: Cobalt(II), Nickel(II), Copper(II), Complex.
252
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P-439
Insitu polymerization of ε-caprolactam in presence of ammonium polyphosphate
toward fire retardant polyamide6 composite
b
Azam Mohammadi*,a, Shervin Ahmadib, Mohammad Usefia, Sima Habibia
a
Islamic Azad University,shahr-e Rey
Department of Polymer Processing, Iran Polymer and Petrochemical Institute, Tehran, Iran
([email protected])
In this study, polymerization of ε-Caprolactam toward fire retardant Polyamide6 composite, in
presence of ammonium polyphosphate via anionic polymerization, during melt mixing was study.
Review the results of mechanical tests showed that in samples which contain ammonium
polyphosphate against the pure matrix, modulus increased and elongation at break decreased.
Residual monomer content of samples had shown that increasing amount of fire retardant, increase
level of residual monomer content. Furthermore, LOI, ASTM D635 and UL94 test results show that
samples that contain higher percentage of ammonium poly-phosphate showed increase fire
retardancy of samples.
Keywords: fire retardant, insitu polymerization, ε-caprolactam, ammonium polyphosphate, residual
monomer.
P-440
Regioselective Aldol Condensation using Keggin Heteropolyacid Catalysts
Ali R. Mohammadi hamaneh, Masoumeh Tabatabaee*
[email protected]
Department of Chemistry, Islamic Azad University Yazd Branch, Yazd, Iran
Heteropolyacids are widely used in variety of acid catalyzed reactions. Heteropolyacids as solid acid
catalysts are green with respect to corrosiveness, safety, quantity of waste, and separability and it
is well known that the use of heteropolyacid catalysts for organic synthesis reactions can give a lot
of benefits. One of the unique features that make solid heteropolyacids economically and
environmentally attractive is their stability and Bronsted acidity. The aldol reactions is one of the
most powerful methods the formation of C-C bondsin organic synthesis and they are widely applied
for the preparation of β-hydroxy aldehydes, β -hydroxy ketones or α,β-unsaturated aldehydes or
ketones through addition or addition-elimination reactions of aldehydes and ketones. Here in, we
present our investigation of aldol condensation using Keggin type heteropolyanion catalysts, in
various conditions. When the mixtures of acetophenone derivatives with various aldehydes in the
presence of catalytic amounts of heteropolyacids in solvent were refluxed in specific times, aldol
condensation products were obtained in high yields. The most important feature of the reactions is
preparation of trans isomers. All synthesized compounds were characterized by elemental, IR and
NMR spectroscopy and the effects of various parameters such as amount of catalysts, solvent and
time were studied.
Keywords: Aldol condensation, Heteropolyacids, catalytic synthesis
IICC12
253
P-441
Synthesis of Novel 1,3,5-triarylpyrazoline Derivatives by High-Surface-Area Cs Salt
Nanocrystals of Phosphotungestic Acid
E. Mohammadi, R. Fazaeli* and H. Aliyan
The elimination by HF of the silica matrix from the composites obtained by the two-step reaction
deposition of Cs2.5H0.5PW12O40 (CsHPW) salt nanocrystal. We have used 2D hexagonal SBA-15 silicas
as templates for the nanofabrication of CsHPW nanoparticles. We have developed an efficient
strategy for the synthesis of 1,3,5-triaryl pyrazoline using CsHPW nanoparticles, as an eco-friendly,
inexpensive and efficient catalyst. The advantages of this catalytic system is mild reaction
conditions, short reaction times, high product yields, easy preparation of the catalysts, non-toxicity
of the catalysts, simple and clean work-up of the desired products.
Keywords:
Nanocasting,
Polyoxometalates (POMs).
Nanoparticles,
Green
chemistry,
1,3,5-triaryl-2-pyrazoline,
P-442
The tridentate Schiff base compounds of 2-aminophenol: synthesis, characterization
and complexation with IIIA elements
Khosro Mohammadi*, Mansooreh Zahedi
Chemistry Department, Faculty of Science, Persian Gulf University, Bushehr 75169. I.R. Iran
*Email: [email protected]; [email protected]
Schiff bases are one of the most versatile classes of ligands for the study of the coordination
chemistry of transition metals. Their ease of synthesis (by the condensation of an aldehyde/ketone
with an amine), multidenticity (from mono to hexadentate), combination of donor atoms
(coordination usually through the imine nitrogen and other atoms like oxygen, sulfur or nitrogen)
and stability have made them the preferred ligand systems in catalysis, biological modelling, the
design of molecular ferromagnets, and as liquid crystals. In this study, we have described synthetic,
spectroscopic and formation constant measurements of a series of IIIA elements with some new
tridentate Schiff base ligands which have been characterized by elemental analysis, IR, Mass
spectroscopy and 1HNMR spectrophotometry. The comparison of formation constants and the
thermodynamic parameters show that the trend of formation constants of metal ions with these
ligands.
Keywords: Schiff base, 2-Aminophenol, Tridentate, Formation constant.
254
IICC12
P-443
Synthesis and characterization of a new tetradentate Schiff base of 2 aminophenol and
complexation with some metal ions
Khosro mohammadi *, Mansooreh Zahedi
Chemistry Department, Faculty of Science, Persian Gulf University, Bushehr 75169, I.R.Iran
*Email :[email protected], khmohammadi @yahoo.com
Schiff bases have played an important role in the development of coordination chemistry
because of their distinct advantages such as ease of synthesis; low cost as well as variety
of coordination sites, as they readily form stable complexes with most transition metals. A
lot of attention has been recently devoted to the tetradentate Schiff bases and their
complexes. Such complexes have been employed as catalysts for many reactions and as
biological models in understanding the structure of biomolecules and biological processes.
The present study deals with the synthesis and characterization of a new tetradentate
Schiff base from 2-aminophenol
with isophethaldyaldehyde and their chelates with some
transition metal ions, e.g. Zn(II), Co(II), Ni(II) and Cu(II).The ligand and its complexes
have been synthesized and characterized by elemental analysis, IR, Mass spectroscopy
and 1HNMR spectrophotometry. And also, the formation constant of the ligand with metal
ions were measured by spectrophotometric method which shows good interaction
between them.
Keywords: Schiff base, 2-Aminophenol, Tetradentate, Formation Constant.
P-444
New Pyrimidine Schiff base compounds and their complexes with IIIA metal ions:
synthesis, characterization and thermodynamics.
Khosro Mohammadi*, Mohamad Ramin Bastan
Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, I. R. Iran
Email :[email protected], khmohammadi @yahoo.com
In Schiff base metal complexes, the environment at the coordination center can be modified by
attaching different substituents to the ligand, which provides a useful range of steric and electronic
properties essential for the fine-tuning of structure and reactivity. Therefore, Schiff base ligands are
among the most fundamental chelating systems in coordination chemistry and complexes of both
transition and p-block metals based on this type ligands have been shown to catalyze a wide variety
of reactions. Pyrimidine derivatives constitute a very important class of compounds because they
are components of nucleic acids and have been shown to exert a pronounced physiological effect.
The pyrimidine ring represents one constituent of nucleic acid, vitamins, coenzymes and antibiotics
and provides potential binding sites for metal ions. The coordination properties of pyrimidines are
important in understanding the role of metal ions in biological systems. Metal complexes of purines,
pyrimidines and their nucleotides play a dominant role in many biochemical systems. In this study,
a series of tridentate Schiff bases with 2,4-diamino-6-hydroxypyrimidine as amine, were synthesized
and characterized by HNMR and FTIR spectroscopy. Also, trivalent metal hexa-coordinated Schiff
base complexes with Ga3+, In3+, Tl3+ were synthesized and the interactions with the metal ions were
studied.
Keywords: Pyrimidine; Schiff base; Gallium; Indium; Thallium; Complex formation.
IICC12
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P-445
Synthesis and application of orthopalladated complex of 4phenylbenzoylmethylenetriphenylphosphorane as a high active catalyst in the Suzuki
cross-coupling reaction
M. Mohamadi Salah*, K. Karami *, C. Rizzoli**
*Department of Chemistry, Isfahan University of Technology
**Dipartimento di Chimica Generale ed Inorganica, University of Parma, Italy
The Ortho-metalated complex [Pd(µ-Cl){κ2(C,C)-[C6H4(PPh2CHC(O)C6H4-Ph-4)}]2 can be prepared
of Pd(OAc)2 and {(Ph)3PCHCOC6H4-Ph-4} (PhBPPY) followed by addition of an excess of KCl.
Complex
reacts
with
triphenylphosphine
to
give
the
mononuclear
derivative
[Pd(Cl)(PhC6H4COCHPPh2C6H4) (PPh3)] whose crystal structure has been determined by single
crystal X-ray diffraction. Complex is fairly effective in Suzuki cross-coupling reaction to give the
products in good to excellent yields in most cases. Pd-catalyzed cross-coupling reactions are ranked
today among the most general transformations in organic synthesis, which have great industrial
potential for the synthesis of chemicals, therapeutic drugs, and their intermediates. Palladiumcatalyzed Suzuki cross-coupling reactions of aryl halides with arylboronic acids have emerged as an
extremely efficient and important tool in organic synthesis, as well as in a variety of industrial
processes. Herein, we wish to report the high yield in the Suzuki cross-coupling reaction of
phenylboronic acid with some aryl-halides.
Keywords: Ortho-metalated, Suzuki reaction, Cross-coupling, Palladium-catalyzed.
P-446
One-pot synthesis of dihydropyrimidinones using [Cu(2,2′-bipy)][Cu(2,2′bipy)2]2[PMo8V6O42]. 1.5 H2O as catalyst for the Biginelli reaction
F. Mohammadifar, R. Fazaeli* and H. Aliyan
Recently, much work has been focused on the rational construction of new organic–inorganic
complexes based on polyoxometalates (POMs) and transition metal complexes (TMCs) due to their
intriguing structures and potential applications in many areas. In these complexes, POMs can
coordinate to "secondary" transition metal atoms with organic moieties using their terminal or
bridging oxygen atoms to stabilize frameworks. The dihydropyrimidinone derivatives have attracted
considerable interest in recent years due to promising activities as calcium channel blockers, and as
antihypertensive, antibacterial, antitumor and anti-inflammatory agents. In continuation of our
previously reported catalytic properties of heteropoly acids, (HPAs), herein, we wish to report a
suitable method for the use of Keggin molybdenum–vanadium clusters and copper complex
fragments as catalyst for the Biginelli reaction.
Keywords: Hydrothermal synthesis, Metal complex fragment, Keggin-type polyoxometalate.
256
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P-447
Complexation of the Transition Metals with Unsymmetrical N2O2 Schiff Base Ligands
Maryam Mohammadikisha,*, Mozaffar Asadib, Khosro Mohammadic
Chemistry Department, Islamic Azad University-Kermanshah branch
([email protected])
b
Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, I. R. Iran
c
Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, I. R. Iran
a
Schiff bases are very important tools for the inorganic chemists as these are widely used in
designing molecular ferromagnets, in catalysis, in biological modeling applications and as liquid
crystals. Schiff base complexes are known to be biologically important and serve as catalysts in
various chemical and photochemical reactions. In this study by using a tetradentate N2O2 Schiff
base ligands system, we have succeeded in preparing four coordinate Mn(II), Co(II), Cu(II) and
Zn(II) complexes containing 2-aminobenzylamine and substituted salicylaldehyde. The effect of the
nature of the equatorial substituent on the ligands upon the UV-Vis bands was studied. By
considering the formation constants and the ∆G˚ of the complex formation for Schiff base as donor
and the M(II) as acceptor, the following conclusions were drawn:
1. The formation constant for a given Schiff bases changes according to the following trend:
Mn(II) < Zn(II) < Co(II) < Cu(II)
2. The formation constants for a given M(II) acceptor toward the Schiff base donors changes
according to the following trend:
5-OMe > 5-H > 5- Br > 5- NO2
Keywords: Schiff base, Formation constant, Manganese, Cobalt, copper, Zinc
P-448
Synthesis and characterization binuclear of tin complexes of bis tridentate (ON0,
ONN)Schiff base ligands
Farahnaz mohammadloa,*, A.H. Kianfar b and, Mehrnosh Kiani a
Department of Chemistry, Islamic Azad University of Gachsaran Branch
b
Department of Chemistry, University of kohgiloyeh boyerahmad, Yasouj ,Iran
a
The schiff bases have been widely used as ligands because of high stability of the coordination
compounds and their good solubility in common solvents.Thermo chemical properties of Schiff
bases have attracted much researcher attention in view of their ability to coordinate metal ions,
acting as bis tridentate ligands in metal chelates involving ONO or ONN Schiff-base donor atom
sets. These Schiff base metal derivatives have considerable interest due to their role as model
complexes to biological systems, contributing to the knowledge of their structure and behavior.In
this work Schiff base ligands were prepared in two step. The first step 4,6-Diacetylresorcinol was
prepared as cited in literature. The second step was the condensation of 4,6-Diacetylresorcinol
(DAR) stoichometrecally in a molar ratio 1:2 with 2-amino phenol and 1,2-phenyl di amine
derivatives, in methanol. The tin complexes were synthesized by reaction 2mol of (Bu2SnO) with
1mol of the ligands in methanol. Structure of the ligands and complexes were characterized on the
basis of their, elemental analysis, melting points, IR,1H NMR and UV–Vis spectra. The IR spectra of
the complexes are compared with that of the free ligand to determine the changes that might have
taken place during the complexation. Also, the band at 2900 cm–1 assinged to buthyl groups in the
complexes.
Keywords: Binuclear of tin complexes; 4,6-Diacetylresorcinol; 2-amino phenol; bis tridentate
ligand
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257
P-449
Novel complexes of Cadmium(II) and Zinc(II) with 4,4'-Dimethyl-2,2'-Bipyridine and
6,6'-Dimethyl-2,2'-Bipyridine; Synthesis, Characterization and Crystal Structure
Determination
a
P. Mohammdi Eshlaghia, R. Alizadeha,*
Much attention is given to bipyridine (Bpy) systems because of their central role in the fields of
inorganic, organometallic, and coordination chemistry. Bpy ligands generally afford efficient binding
affinity for most elements in the periodic table due to the chelation effect and the π-accepting
ability of these moieties. In general inorganic-organic hybrid materials have been of great interest
because of their intriguing structural features and potential in various applications. In fact,
compounds containing IIB elements are particularly attractive for many reasons: the variety of
coordination numbers and geometries provided by the d10 configuration of the IIB metal ions,
photoelectric properties, fluorescence properties, widespread applications of IIB compounds, the
essential role in biological systems of zinc, and so on. In this work, two novel complexes of zinc(II)
and cadmium(II) with 4,4′-dimethyl-2,2′-bipyridine and 6,6′-dimethyl-2,2′-bipyridine ligands were
synthesized from the reaction of ZnBr2 and CdCl2 with these ligands. Both complexes were
thoroughly characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy and single-crystal
X-ray diffraction methods.
Keywords: Crystal Structure; Cadmium (II); Zinc (II); 4,4′-Dimethyl-2,2′-bipyridine; 6,6′-Dimethyl2,2′-bipyridine
P-450
Fabrication of nickel hydroxy/oxide nanostructures via a thermolysis of of metalorganic frameworks
a
F. Mohandes a, M. Salavati-Niasari a,b*
Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran.
b
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, Iran
This paper reports the synthesis of nickel hydroxy/oxide nanostructures via the thermolysis of
[Ni(Pht)(H2O)]n polymers, which were prepared simply by a wet-chemical precipitation. Nickel
hydroxy nanostructures with rhombohedral lattice were produced through thermolysis of polymers
in the presence of fatty acid but by using triphenylphosphine (TPP) at higher temperature, NiO
nanoparticles with cubic lattice were formed. FT-IR, X-ray diffraction (XRD), scanning electron
microscopy (SEM) and transmission electron microscopy (TEM) analyses were applied for the
characterization of products. It was found that the particle size, morphology and chemical
composition are vigorously dependant on the reaction conditions such as: the type of surfactants or
refluxing temperature. The XRD patterns and TEM images showed that the particle size of nickel
hydroxy nanostructures and NiO nanoparticles was about 7-10 nm and 35-40 nm, respectively. We
expect that this approach would be a promising route to synthesize some other metal oxides and
metal hydroxides with various nanostructures.
Keywords: Chelating Bidentate Ligand, Nanostructure, Nickel Hydroxyl/Oxide, Polymers.
258
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P-451
Influence of Temperature and Ultrasonic Power on the Crystallinity of Hydroxyapatite
Nanoparticles Synthesized by Sonochemistry
M. Mohebali* and A. Shokuhfar
Advanced Materials and Nanotechnology Lab, Department of Mechanical Engineering, K.N. Toosi
University of Technology, Tehran, Iran
([email protected])
Due to its similarities with the inorganic component of bone and tooth, hydroxyapatite
(Ca10(PO4)6(OH)2) has been extensively studied for biomedical applications. In this study,
hydroxyapatite nanoparticles were synthesized by the aid of ultrasonic irradiation and from an
aqueous suspension containing calcium hydroxide (Ca(OH)2) and phosphoric acid (H3PO4). The
reagents were introduced to coincide to the stoichiometric hydroxyapatite Ca/P molar ratio of 1.67.
Ammonium hydroxide (NH4OH) was then added to the aqueous suspension to increase the pH (up
to 9). The influence of processing temperature and ultrasonic power on the crystallinity and size of
the prepared particles were investigated by X-Ray diffraction (XRD) patterns. The results indicated
that sonochemistry could be a suitable route for preparation of hydroxyapatite nanoparticles for
biomedical applications. In addition, increasing the ultrasonic power decreased the particle size and
increasing the temperature improved the crystallinity.
Keywords: Hydroxyapatite, Nanoparticle, Sonochemistry, Crystallinity.
P-452
Synthesis and solvatochromism studies of mixed-chelate copper(II) containing 3chloroacetyactonate and N-((furan-2-yl)methyl)-N,N’-dimethylethane-1,2-diamine
Ligands
Z. Mohseni afshar, F.izadi amoli and H. Golchoubian
(e-mail: [email protected] ,[email protected], [email protected])
Solvatochromism is defined as the pronounced change in position and sometimes intensity of an
electronic absorption or emission band accompanying with a change in the polarity of the medium.
This phenomenon can be even detected visually by the change in the color of the solution when the
solvent is varied. Copper(II) complexes of ethylenediamine derivatives with N-methyl and N-ethyl
groups are rather well known , but little has been reported on those with higher steric hindrances.
Recently we prepared mixed-chelate copper(II) complex shown below that is solvatochromic.
These complexes are soluble almost in a large number of solvents and show negative
solvatochromism. Solvatochromism study of they complexy performed by visible spectroscopy
technique. This report shows syntheses and characterization of new copper(II) complex along with
the synthesis and characterization of new N-((furan-2-yl)methyl)-N,N’-dimethylethane-1,2-diamine
ligand.
Keywords: Solvatochromism, Copper (II) complex, Mixed-chelate complex, Chloroacetylacetonate
ligand, N,N.N’ derivative of ethylenediamine.
IICC12
259
P-453
Synthesis, characterization ,antibacterial and oxidation properties studies CoPhthalocyanine
a
Sh. Mohsenierada, G. Geimachya, Sh.Ghammamy *, b Kh. Mehrania and A. Parchebafa
b
E-mail: [email protected] or [email protected]
Phtalocyanines are important compounds specially Cobalt Phtalocyanine or Merox that recently
utilizing them have been much frequent in many countries. This compounds have many uses. One
of their important implieations is elimination Mercaptan in petroleum industry. In this study; a new
compound was produced from phtalocyanine with general formula MTsPc, (M=Co)[1-4]. This
compound was studied by FT-IR and UV/Vis spectroscopes and molecular structure of the
compound was anticipated by this way. Also oxidation properties of eight alcohols (1-Butanol, 1Propanol, 2-Butanol, Benzyl Alcohol, Ethanol, Isobuthyl Alcohol, Isopentyl Alcohol and
Cyclohexanol) were surveid by this comound. Their biologieal properties (cancer and bacteria test)
were examined. In the meanwile Nono technology was done on this compound.
Keywords: Phtalocyanine, Cobalt Phtalocyanine, FT-IR, UV/Vis, molecular structure, oxidation
properties, Nono technology
P-454
Synthesis and Characterization of Some Biologically Relevant Iminophenolate
Copper(II) Complexes
M. Mohsenikabir, E. Safaei*
Galactose oxidase is an enzyme that catalyses the oxidation of primary alcohols to aldehydes. The
active site of this enzyme contains a water molecule, two tyrosine and two histidine residues
coordinated to a copper (II) center. Extensive efforts have been made to provide valuable insight
into the structure and reactivity of galactose oxidase active site. In this work, a series of novel
bis(N- aryl(alkyl)- 3, 5- di- tert- butylsalicylaldiminato) copper(II) and bis(N- aryl(alkyl)- 5- di- tertbutylsalicylaldiminato) copper(II), have been prepared and their spectroscopic (IR, UV-vis, ESIMS), X- ray, magnetic and redox properties have been investigated. The X- ray analysis shows that
all complexes are monomer and their copper(II) centers have been surrounded by two phenolate
oxygen and two imine nitrogen atoms. The molecular geometries of complexes are square plannar
or slightly distorted square plannar. The crystal systems of complexes are orthorhombic or
monoclinic. Magnetic susceptibility measurement of all complexes revealed paramagnetic
properties, except in one case with slightly antiferromagnetic interlayer exchange. Oxidation of the
Cu(II) complexes yielded the corresponding Cu(II)- phenoxyl radical species during the cyclic
voltammetry experiments as models for Cu(II)- tyrosyl radicals in galactose oxidase.
Keywords: Galactose oxidase, Model complexes, Cyclic voltammetry, Iminophenolate
260
IICC12
P-455
Synthesis and characterization some new Mercury(II) Coordination polymers with
nitrogen donor ligands:
a
Nehleh mojahedia , Mohammad Jaafar Soltanian Farda* , Ali Morsalib
Department of Chemistry, Islamic Azad University, Firoozabad branch, Firoozabad,Fars, Iran
b
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran, Iran
([email protected])
Some new Mercury(II) coordination polymers with nitrogen donor ligands such as 3,5 bis(2pyridyl),4-amino,1,2,4-tri azol(2-abpt) and 3,5 bis(4-pyridyl),4-amino,1,2,4-tri azol(4-abpt) has been
synthesized using branched tube and reflux method and characterized by CHN elemental analysis,
IR, 1H NMR,UV-Vis spectroscopy and studied its thermal behavior as well as X-ray crystallography,
respectively. The thermal stability of compound was studied by thermal gravimetric analysis(TGA)
and differential thermal analysis(DTA) diagrams too.
Keywords: Mercury(II) , Nitrogen donor ligand, Coordination polymers,
P-456
Calculation and prediction structure of novel complexation of porphine and TiCl4
M. Mojiri Foroushani, H. Dehghani*
Using various theoretical methods, the complexation of TiCl4 as a Lewis acid with free base porphine
(Donor–acceptor complexes) has been investigated. To dig into stability trends, total electronic
energies of final optimized structures calculated at various levels have been offered in research. It
is clear that regardless of the method and basis set used, the one bonded structures are stable than
their two bonded isomers. However, assuming mentioned information, it is obvious that between
two bonded structures, the cis isomer is more stable than trans shape. At B3LYP/6-31G(d) level,
formation of por-(TiCl4)2 from por-TiCl4 and TiCl4 are accompanied by the energy increase of 240.5
and 191.8 kcal mol-1, for trans and cis isomer, respectively. On the other hand, addition of the first
TiCl4 molecule to the trans and cis porphine releases 327.2 and 377.2 kcal mol -1, respectively.
Similar results are found from other calculations. The higher energy of stability (86.7 and 185.4 kcal
mol-1) for addition of the second TiCl4 to the 1:1 adduct as in comparison to the addition of a TiCl4
molecule to a free base porphine presumably reflects the greater tendency of the free porphine
than 1:1 adduct for coordination with a TiCl4 molecule.
Keywords: Porphine; theoretical methods; TiCl4; Donor–acceptor complexes
IICC12
261
P-457
Stabilization of Transition Metal complexes with Nitrogen- rich Donor Ligands
S. Mokhtari Dehkordi, M. Tayebani*
Department of Chemistry, Islamic Azad University, Shahreza Branch, Isfahan, Iran
Nitrogen-rich energetic compounds contain N-N and C-N bonds. These kind of energetic compounds
have high nitrogen content, high positive enthalpy and big explosive heat. By decomposition of
nitrogen-rich compounds enormous energy are released. These kinds of compounds are widely
applied in the field of energetic materials, such as insensitive high explosive, low signal propellants,
gas forming agents and pyrotechnics. At present, nitrogen–rich energetic compounds have been a
hotspot in energetic materials worldwide. Many of the reported nitrogen-rich compounds are based
on C/N heteroaromatic cycles, including pyrimidines, triazoles, tetrazoles, triazines, tetrazines, and
heptazines. Due to the high applications of nitrogen-rich compounds we are interested in the
transition metal complexes of this type and study their reactivity. Here in, we report the synthesis
of Co(II) and Ni(II) complexes of N,N’-diphenyloxalic (bishydrazide) and N,N’-diphenylethane (bishydrazonol dichloride).
Keywords: N,N’-diphenyloxalic, N,N’-diphenylehane, Nitrogen-rich, Tetrazine
P-458
Synthesis and characterization of nanocrystalline NiS by chemical reduction process
H. Molaei and S. A. Kahani*
Department of Inorganic chemistry, Faculty of Chemistry, University of Kashan, Iran
Nickel sulfides have important applications as hydrogenation catalysis, among which NiS and Ni3S2
have been reported as the most important ones in terms of catalytic activity. Nickel sulfide can be
prepared in the laboratory by precipitation from an aqueous solution of a nickel salt with
ammonium sulfide, (NH4)2S, or by precipitation from an acetic acid solution with hydrogen sulfide.
Nickel sulfide also can be prepared by reacting nickel powder with molten sulfur. Here we propose a
new method in preparation of Millerite (γ-NiS) nanocrystals. It is prepared through the chemical
reduction of nickel diethyldithiocarbamato complex using sodium hydroxide as alkaline reagent and
hydrazine monohydrate (N2H4.H2O) as reducing agent at 100° C and PH=10-12. The reaction is
taking placed at 6 hours the products are NiS and Ni3S2 (a), when the time of reaction increase to
10 days the product is only γ-NiS (b). X-ray powder diffraction (XRD) and scanning electron
microscopy (SEM) were used to characterization of the products. XRD pattern indicated that the
products of (a) condition are NiS and Ni3S2 nanoparticles with crystalline size of 37 nm and 35 nm
respectively and with (b) reaction conditions only pure γ-NiS nanocrystals is formed that the
average crystalline size of NiS is 17 nm. Interestingly, the SEM image reveals that the NiS has a
particle size with the average size of 40 nm. In summary, we have successfully synthesized γ-NiS
nanocrystals via a chemical reduction route with crystalline size of 17 and particle size 40 nm.
Keywords: Nanocrystalline, Nickel sulfides, Hydrazine hydrate, X-ray powder diffraction.
262
IICC12
P-459
Synthesis and characterization of Fe3O4 nanoparticles using diamine hydrate by
chemical reduction route
H. Molaei, A. Kahani*
Department of Inorganic chemistry, Faculty of Chemistry, University of Kashan, Iran
Magnetite (Fe3O4) nanoparticles have received much attention for their applications in various fields
of medical care such as drug delivery system, cancer therapy, and magnetic resonance imaging.
Fe3O4 forms the cubic spinel structure, where one-third of the Fe ions occupy the A sites which are
trivalent, while the remaining two-third on the B sites are mixed valence with formal average
valence Fe2.5+. Chemical reduction process was successfully used to synthesize Fe3O4 nanoparticles
using iron (III) sulfate, diamine hydrate (N2H4.H2O) and ammonia as starting materials and reaction
take placed at 90°C and PH= 10-12. The particle size, morphology, and magnetic properties of the
products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy
(SEM), and vibrating sample magnetometer (VSM). The XRD patterns indicated that the products
were pure magnetite and the average crystalline size of Fe3O4 is 12 nm. The magnetic properties of
the nanoparticles exhibited a superparamagnetic behavior at room temperature. As a conclusion,
Fe3O4 nanoparticles were prepared by the chemical reduction of Fe3+ ions by a reducing agent
(N2H4.H2O).
Keywords: nanoparticles, magnetite, Chemical reduction, Diamine hydrate, Magnetic properties
P-460
Synthesis, Characterization and Electrochemistry of New Schiff base Co(III)
Complexes; The Crystal Structure of [CoIII(L)(N-MeIm)2]BPh4
Hajar Molaiea, Mehdi Amirnasra*, Soraia Meghdadia, Kurt Mereiterb, Ahmad Amiria
a
Department of Chemistry, Isfahan University of Technology, Isfahan, Iran.
b
Faculty of Chemistry, Vienna University of Technology, Getreidemarkt, Vienna, Austria
Schiff base complexes have been used as drugs and usually show a wide variety of antimicrobial
activity against bacteria, fungi, and certain type of tumors. A new and rare series of cobalt(III)
schiff base complexes with N4 donor ligand of 2-pyrrole carboxaldehyde with the general formula
of trans-[CoIII(L)(amine)2]X {L2– =Schiff base ligand , and amine = N-methylimidazole (N-MeIm)
(1), 3-methylpyridine (3-MePy) (2), 4-methylpyridine (4-MePy) (3), pyridine (Py) (4), X = BPh4⎯}
have been synthesized and characterized by elemental analyses, IR, UV–Vis, and 1H NMR
spectroscopy. The structure of compound 1, was determined by X–ray crystallography and was
found to have a distorted octahedral geometry around Co. Electrochemical studies reveal that the
first reduction process CoIII/CoII is irreversible and strongly influenced by the nature of the axial
amines. The CoIII/CoII reduction potential values, show that stronger axial ligands shift the reduction
potentials to more negative values.
Keywords: Schiff base complexes, Cobalt(III), 2-pyrrole carboxamide, Crystal structure,
Electrochemistry.
IICC12
263
P-461
Sonocatalytic epoxidation of hydrocarbons by manganese tetraphenylporphyrin
supported on multi-wall carbon nanotubes
Maryam Zakeri, Majid Moghadam*, Iraj Mohammadpoor-Baltork, Valiollah Mirkhani, Shahram
Tangestaninejad
Oxidation reactions such as epoxidation are essential in organic synthesis. Metalloporphyrins are
arguably the least known heterogenous catalyst family for alkene epoxidation. Synthetic manganese
porphyrins have been found to achieve high selectivity and reusability in the epoxidation of both
cyclic and linear alkenes. Metaloporphyrins readily undergo decomposition (due to self oxidation) in
solution phase. Therefore attachment of these catalysts to insoluble supports is particularly
attractive as it should prevent this deactivation process. Further advantages of immobilization
include simplified procedures for product purification and catalyst recovery. An important
disadvantage associated with heterogenous catalytic systems is their lower catalytic activity in
comparison with homogenous counterparts. In most cases the use of ultrasonic (US) wave
(sonocatalisis) is recommended for solving this problem. In this paper, the biomimetic epoxidation
of hydrocarbons catalyzed by tetraphenylporphyrinatomanganese(III) chloride [Mn(TPP)Cl]
immobilized on functionalized multi-wall carbon nanotubes is reported. The catalyst ,[Mn(TPP)ClMWCNT], was used as an efficient and hetrogenous catalyst for epoxidation of alkenes by NaIO4 at
room temperature under ultrasonic irradiation. This catalyst was characterized by elemental
analysis, FT-IR spectroscopy, diffuse reflectance UV-Vis spectrophotometry, scanning electron
microscopy and transmission electron microscopy. The biggest advantage of Mn(TPP)Cl-MWCNT is
its high reusability in the oxidation reactions, in which the catalyst was reused several times without
significant loss of its catalytic activity.
Keywords: Epoxidation, Mangannese porphyrin, Carbon nanotube, Ultrasonic wave
P-462
Biomimetic and Environmentally Benign Oxidation of Sulfides using Urea Hydrogen
Peroxide Catalyzed by Molybdenum Schiff Base Complexes
N. Monadi,a,b A. Rezaeifard,a* I. Sheikhshoaeib
Department of Chemistry, , Shahid Bahonar University of Kerman, Kerman, Iran
a
b
Sulfoxides and sulfones play important roles in industry as intermediates for the production of fine
chemicals as well as pharmaceuticals. With respect to environmental and economical
considerations, the applied oxidant determines to a significant extent the value of the system. Thus,
the combination of hydrogen peroxide with a non-toxic and inexpensive metal source constitutes
ideal system sulfoxidation reactions, especially in liquid phase processes in industry. The significant
enzymatic role of molybdenum in biochemical reactions especially in the oxidation of aldehydes,
purines and sulfides induced the chemists to use the molybdenum complexes as biomimetic
catalysts in the oxygenation of organic compounds. In this work, the oxidation of sulfides using UHP
under the catalytic influence of [MoO2LCH3OH] complex in ethanol under mild conditions has been
described. The high/excellent selectivity of this oxidation method combined with the use of UHP and
ethanol as green oxygen source and solvent respectively, makes it more attractive for oxidation of
sulfides to both sulfoxides and sulfones. The promising results for stability of the Mo-Schiff base
complex and high turnover rates obtained in the oxidation reactions highlight the novelty of this
oxidation system.
Keywords: Biomimetic, Hydrogen Peroxide, Oxidation, Sulfoxide, Sulfone, Schiff base
264
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P-463
Synthesis, Spectroscopic Investigation, Thermal Analysis and Biological Activity of New
Diorganotin(IV) Complexes with Schiff Bases Derived from β-diketones
a
M. Monajjemzadeha, T. Sedaghat a,*, H. Motamedib
b
Department of Biology, Shahid Chamran University, Ahvaz, Iran
In the area of bioinorganic chemistry, Schiff bases and their complexes play an important role
because of the medicinal, physiological and pharmaceutical applications. They are well known as
antibacterial, antifungal, anticancer and antiviral agents. Recently, increasing attention has been
devoted to Schiff base complexes of organotin(IV) moieties in view of their chemical properties,
biological significance, industrial importance and structural variety. Organotin (IV) complexes
possess intrinsic properties that promise them for the creation of new materials and new metalbase drugs. In this research work, the new organotin(IV) complexes [SnPh2(La)], [SnPh2(Lb)],
[SnPh2(Lc)] and [SnMe2(Lc)] have been synthesized from reaction of diorganotin(IV) dichlorides with
Schiff bases H2La, H2Lb and H2Lc, derived from condensation of 2-amino-4-chlorophenol with
acetylacetone, benzoylacetone and dibenzoylmethane, respectively. These compounds were
characterized by elemental analysis and FT-IR, 1H, 13C and 119Sn NMR spectroscopy. On the basis of
these data, Schiff base acts as a tridentate dianionic ligand and coordinates through enolic oxygen,
imine nitrogen and phenolic oxygen. The coordination number of tin is five. Thermogravimetric
studies reflect the thermal stability of complexes. The antibacterial activity evaluation of Schiff
bases and complexes against two Gram-positive and two Gram-negative bacteria exhibited they
have a potential to be used as drugs.
Keywords: Diorganotin(IV), Schiff base, Diketones, Thermal analysis, Antibacterial activity
P-464
Hydrothermal synthesis and structure of New Organic-Inorganic Hybrid
polyoxotungstate
A.A. Zamani Cini, R. Fazaeli* and H. Aliyan
Polyoxometalates (POMs) are inorganic metal–oxygen clusters with an enormous structural and
compositional variety. The combination of transition metal complexes and POMs could provide new
organic–inorganic complexes with novel structural types, as well as new properties arising from the
interplay of the two components, which can be used as effective functional materials. The grafting
of the organic moieties into vacant POMs is of great interest, especially for insoluble organic
ligands, by using a general method under mild conditions. Furthermore, the functionalization of
Keggin POMs with organic moieties is of special significance because of their numerous applications.
Thus, this strategy may lead to hybrid multifunctional materials, as for example, those combining a
magnetic component with organic conducting molecules. Herein, we report a new organic-inorganic
hybrid material, prepared under hydrothermal conditions from a mixture of H3PW12O40, nH2O,
CuSO4.5H2O, Schiff-base ligand (H2hacac), Na3VO4. 2H2O and H2O at 160 oC for 5 days. This
organic-inorganic hybrid material is suitable catalyst for One-pot synthesis of dihydropyrimidinones.
Keywords:
Organic-Inorganic
Polyoxometalates (POMs).
Hybrid,
Schiff-base
ligand,
Hydrothermal
synthesis,
IICC12
265
P-465
Hydroxylation of benzene to phenol with hydrogen peroxide over vanadium substituted
heteropoly acid encapsulated on de-aluminated Y zeolite
S.R.Moosavikia, A.Nemati kharat*
School of Chemistry, university college of science, University of Tehran, Tehran, Iran
([email protected])
Extensive research is currently underway to develop supported Molybdovanadophosphoric acid (VHPA) due to their oxidation activity and easier recovery in liquid phase reactions. Many of usual
supports such as SiO2, MCM-41, SBA-15 and zeolites have been studied. In this work
Molybdovanadophosphoric has been encapsulated in the super cage of dealuminated Y-type zeolite
by the” ship in the bottle” synthesis. Resulted supported Molybdovanadophosphoric acid was
compared with similar products from conventional impregnation method. XRD analysis of supported
heteropoly acid show the same diffraction patterns of the support, possibly due to a high dispersion
of non-crystalline species. UV -visible, FT-IR and TGA data confirm the incorporation of
molybdovanadiumphosphoric acid on to the supports. Also surface area of catalyst has been studied
by nitrogen adsorption studies. Catalytic activity of prepared catalyst in oxidation of benzene to
phenol in present of hydrogen peroxide has been investigated.
Keywords: dealuminated Y zeolite, molybdovanadophosphoric acid, encapsulated, benzene
hydroxylation
P-466
Synthesis and Spectrophotometric Studies of Some Molybdenum Complexes of Folic
Acid
Zeinab Moradi, Davar M. Boghaei*
The prosthetic group of oxomolybdoenzymes (Mo-co) has a pterin (2-amino-4-hydroxypteridine)
derivative proposed to be bound to molybdenum that is supported by spectroscopic and chemical
data. Information on pterin-metal interactions may give clues to the role of metal ions in oxygen
and electron transfer in relevant enzymatic reactions. In order to study the behavior of folic acid
and molybdenum in solutions of different pH, Molybdenum(VI) complexes of folic acid (FA, figure 1)
have been synthesized and examined for their possible interactions at pH=7 and pH>10 that
resulted orange [MoO2(FA)(H2O)] and yellow green [MoO2(FA)(H2O)2], respectively. The complexes
characterized by elemental analysis, atomic absorption, IR, 1H NMR and 13C NMR spectra. The UVVis spectrophotometric results are also in agreement with the formation of a 1:1 complex between
the reactants at these pHs. Distinct chemical shift in 1H and 13C NMR spectra revealed that the
pteridine nucleus of folic acid has been coordinated to Mo(VI) through its O(4), N(5) and side-chain
nitrogen (N(10)) atoms at neutral pH and through the carboxylic groups in glutamic moiety at
alkaline pH. The most characteristic feature of the prepared products is two band of νM=O that
prefers to form a cis-MoO2 structure. The structural diversity encountered in Molybdenum-folate
complexes was attributed to the versatile ligational behavior due to different coordination modes.
Keywords: Enzymes, Oxomolybdenum, Pterin-metal Interactions, Folic Acid.
266
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P-467
Theoretical study of the CO Insertion into the Pt– η1-Cp Bond of [PtCp(I)(CO)(L)] (L =
PMe3, PH3, PCl3, NH3, N-heterocycle carben)
a
Azadeh Moradzadeha,*, Alireza Ariafard b,a, Tahmineh Mehrabia, Zeinab Ezheheea
Deptartment of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University,
Tehran, Iran
b
School of Chemistry, University of Tasmania, Private Bag 75, Hobart, TAS, 7001, Australia
In this project we applied the density functional method at the B3LYP level to evaluate the
mechanism of CO-migratory insertion reaction into a Pt– η1-Cp Bond. We also studied the effect of
various L ligands on the ease of the CO insertion into the(η1-Cp)-Pt bond of [Pt(Cp)(I)(CO)(L)] (L =
PMe3, PH3, PCl3, NH3, N-heterocycle carben). We have proposed two mechanisms for the CO
insertion process and studied the energetic for both variants. Our calculations indicate that the
barriers for the CO-insertion process increase in the following order PMe3<N-heterocycl
Carben<PH3<PCl3<NH3. It was established that the more electron donating phosphine ligands
significantly decrease the CO insertion activation energy barriers and therefore the reaction should
occur faster and easier.
Keywords: CO insertion , CO-migratory insertion reaction
P-468
Tautomerization of the 2-[(2,4-Dimethylphenyl)iminomethyl]-3,5-dimethoxyphenol. A
DFT Study
Ali Morsali*, S. Ali Beyramabadi
Department of Chemistry, Faculty of Science, Islamic Azad University, Mashhad branch, Iran
X-ray analysis indicates that the title Schiff-base compound involves both OH (enol) and NH (keto)
tautomeric forms in its molecular structure. The occupancies of the enol and keto tautomers are
0.62 and 0.38, respectively, and their structures could not be determined experimentally. Here, the
structures of enol and keto forms together with the tautomerization mechanism of the title Schiff
bases ligand have been investigated by employing the density functional theory (B3LYP functional
[2]) at the 6-311+G(d,p) basis set. The solvent effects have also been taken into account by using
the continuum model (PCM) [3] in ethanol solution. The optimized structures of both forms of the
ligand are approximately planar. In both the gas and solution phases, the enol form is more stable
than the keto one. The solvent effects decrease their energies. Also, in comparison to the gas
phase, the energy barrier of enol-keto tatumerism reaction is decreased in the solution phase. The
calculated structural parameters are consistent with the experimental ones, confirming the
suitability of the optimized geometries for the tautomeric forms of the ligand and transition state of
the reaction. Also, the obtained percents for the enol and keto forms are in good agreement with
the experimental ones.
Keywords: Enol-keto tautomerization, Schiff base, DFT, PCM, Transition state.
IICC12
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P-469
Study on Catalytic Activity of Platinum Porphyrins in Oxidation Reactions
a
A. Mortazavi Manesh, N. Safari* and S. Rayati
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran, Iran
Metalloporphyrins are well known to mimic the activity of enzymatic monooxygenases. In this
manner, an extensive amount of research has focused on them owing to the critical roles they play
in catalytic oxidation including hydroxylation and epoxidation of hydrocarbons. Investigating in this
area is based on different strategies to design selective, stable and high turnover catalytic systems.
In the present work, different meso-tetra-arylporphyrinatoplatinum(II) were prepared and used as
catalyst for oxidation of various alkenes in the presence of iodosylbenzene. The results show that
these metalloporphyrins were selected for the reason that they are enough stable and have the
advantage of inhibiting the oxidation degradation. The higher yields of products and stability of
these catalysts especially for PtF20TPP, introduce them as the best candidate among all kinds of
metalloporphyrins in catalytic oxidations. In fact, the majority of the studies are directed to
understanding the mechanism of the catalytic activity of heme containing enzyms such as
cytochrome P-450. The active species is also considered to be a trans-dioxoplatinum(VI) porphyrin
complex. The purpose of this research was to gain insight of the reaction mechanism and
introducing Pt-porphyrins as the best catalysts for catalytic oxidation reactions.
Keywords: Platinum Porphyrin, Iodosylbenzene, Epoxidation, Catalyst, High turn over
P-470
Catalytic oxidation of Phenol by H2O2 over host (zeolite-Y)/ guest (transition metal
salen-schiff base complexes)
Z. Mortezaee, M. Zendehdel* A. Mobinikhaledi
Department of chemistry, university of Arak,Arak,Iran
Considering the catalytic activities of transition metal such as: Cu(II),Mn(II),Co(II),Ni(II) Schiff
base complexes encapsulated in Zeolite-Y is our purpose in work.Transition metal complexes with
tetradendate
Schiff-base
ligand:2,2/-(4,5-dimethyl-1,2-phenylene)bis(azan-1-yl-1ylidene)bis(methan-1-yl-1-ylidene)diphenol.The formed complex was intrapped in the nanocavity of
zeolite-Y by a two-step process in the liquid phase.The formation of Schiff base ligand and zeolite-Y
was confirmed with IR and UV-Vis spectroscopy before complexing,and then the new materials
were
characterized
by
several
techniques:
chemical
analysis,spectroscopic
method(FTIR,DRS,TGA,XRD).Analysis of the data indicates that the M(II)complexes are
encapsulated inThe cavity of zeolite-Y,that the encapsulated complexes are more active than the
neat complexes ,and it could easily be separated From the products and the catalysts can be
reused,without the loss of catalytic activity.
Keywords: Transition metal salen-schiff base complex; Zeolite-Y; Encapsulated; Catalytic activities.
268
IICC12
P-471
Thermodynamic Studies of the Interaction of Nickel(ΙΙ) Schiff Base Complexes with
Diorganotin(IV)dichlorides in Acetonitrile Solvent
Fatemeh Mosalanezhada, Mozaffar Asadib*, Zahra Asadib
Chemistry Department, Islamic Azad University, Jahrom branch, Iran
b
Chemistry Department, College of Sciences, Shiraz University, Shiraz. Iran
[email protected]
a
In the past decades, a large number of transition metal complexes of Schiff base ligands derived
from the condensation of salicylaldehyde and its derivatives with various primary amines become
the hot topics of contemporary research.To find better understanding about the media effects on
the molecular intraction between acceptor-donor systems several investigations have been done.
Nickel Schiff base complexes play an important role in the area of catalysis in agrochemical and
pharmaceutical industries. Several investigations have been done on the molecular structure of the
transition metal Schiff base complexes as ligand for tin chemistry. A Uv-Vis spectrometric study of
the adduct formation of the nickel(II) Schiff base complexes, ([NiL]) where L=[α,ά-Me2-salen, N,N´ethylenebis(α-methylsalicylideneiminate)
(1),
[α,ά-Me2-salpn,
N,N´-1,2-propylenebis(αmethylsalicylideneiminate)](2), [α,ά-Ph2-salen, N,N´-ethylenebis(α-phenylsalicylideneiminate)](3),
[α,ά-Ph2-salpn, N,N´-1,2-propylenebis(α-phenylsalicylideneiminate)](4), as donors with R2SnCl2 (R=
methyl, phenyl and n-butyl) as acceptors have been investigated in acetonitrile, as solvent. The
formation constants and the thermodynamic free energies were measured using Uv-Vis
spectrophotometric titration for adduct formation at various temperatures. The trend of the adduct
formation of the nickel Schiff base complexes with a given tin acceptor decreases as follow: Ni(α,άMe2-salen) > Ni(α,ά-Me2-salpn) > Ni(α,ά-Ph2-salen) >Ni(α,ά-Ph2-salpn). The trend of the reaction of
R2SnCl2 acceptors toward a given nickel Schiff base complex is as follows: Ph > Me > Bu.
Keywords: Diorganotin(IV)dichlorides; Thermodynamic; Schiff base; Nickel(II) complexes.
P-472
Synthesis and characterization of a new symmetrical porphyrin Schif base
N. Mostajabi, G. R. Karimipour*
Department of chemistry, University of Yasouj 75918-74831, Iran
Porphyrins and their derivatives are among the best due to its relevance to cytochrome P-450
enzyme. In this field, extended porphyrin Schiff base ligands and their complexes are appropriate
candidates. There are a few reports about porphyrin Schiff-bases, which are ligands produced by
the reaction of amino-substituted porphyrin and aldehydes. In this work, synthesis of a new
symmetrical Schiff base porphyrin is reported from 5, 10, 15, 20-tetrakis (4-aminophenyl)porphyrin
and salicaldehyde. The ligand is characterized by UV, IR and 1H NMR spectra. Having established
the formation of this porphyrin Schiff base ligand, our next goal is to develop this synthetic
procedure to prepare transition metal complexes of porphyrin Schiff base ligands.
Keywords: Schiff base, Porphyrin, Macrocycle, Metal porphyrin, Salicaldehyde, Synthesis.
IICC12
269
P-473
Synthesis and characterization of Cu(II), Ni(II), Zn(II) and Cd(II) complexes with two
new non-symmetric ligands via Schiff base condensation
a
F. Motavaseliyana, A. A. Dehghani-Firouzabadia,*
Schiff bases have played an important role in the development of coordination chemistry as they
readily form stable complexes with most of the transition metals. Transition metal complexes with
oxygen, nitrogen and sulfur donor Schiff bases are of particular interest because of their ability to
possess unusual configurations, their sensitivity to molecular environments and especially their
promising biological properties. The interest of studying Schiff bases containing ONS donors arose
from their significant antifungal, antibacterial, and anticancer activities. In addition, the presence of
both a hard and a soft donor group in one ligand increases the coordination ability towards hard as
well as soft acidic metals. In the area of bioinorganic chemistry interest in Schiff base complexes
has centred on the role such complexes may have in providing synthetic models for the metal
containing sites in metalloproteins and metalloenzymes. In this work, we describe a series of new
Schiff base complexes from the reaction of potentially pentadentate O2N2S-donor non-symmetrical
Schiff base ligands and related Cu(II), Ni(II), Zn(II) and Cd(II) metal ions. Two free ligands also
have been derived from direct condensation of the 2-(3-aminopropylthio)aniline with 2hydroxybenzaldehyde or 4-bromo-2-hydroxybenzaldehyde. These compounds characterized by
elemental analyses, IR, 1H NMR, 13C NMR and FAB mass spectroscopic methods.
Keywords: Schiff base complexes, Pentadentate ligand, Non-symmetric ligand, Cu(II) complexes
P-474
Zinc(II), Copper(II), Cadmium(II) and Nickel(II) complexes derived from macroacyclic
pentadentate Schiff base ligands
a
F. Motavaseliyana, A. A. Dehghani-Firouzabadia,*
Schiff bases are an important class of ligand in coordination chemistry and find extensive
application in different fields. Metal complexes of N, O and S chelating ligands have attracted
considerable attention because of their interesting physicochemical properties, pronounced
biological activities and as models of the metalloenzyme active sites. It is well known that N, O and
S atoms play a key role in the coordination of metals at the active sites of numerous
metallobiomolecules. Here, we report the synthesis of two new non-symmetric macroacyclic Schiff
base ligands from condensation of 2-(2-aminoethylthio)aniline or 2-(3-aminopropylthio)aniline with
pyridine-2-carbaldehyde and their chelates with some transition metal ions, e.g. Cd(II), Zn(II),
Cu(II) and Ni(II). The Schiff bases and their complexes have been characterized by elemental
analysis, IR, 1H NMR, 13C NMR and MASS spectroscopic methods.
Keywords: Schiff base ligand, non-symmetry ligand. Pyridine, pentadentate ligand
270
IICC12
P-475
Syntheses of Nickel(II) complexes with aminoalkyl bis(o-aminophenol) ligand
Elham Mousavi and Rasoul Vafazadeh*
Mannich-type reactions are one of the most important carbon–carbon bond formation reactions in
compound synthesis. The mannich aminomethylation reactions are multi-component condensation
between chelated metal complexes, non-enolizable aldehyde (commonly formaldehyde) and a
bridging group like nitroalkanes, malonic esters, primary amines, etc. A new nickel(II) complexes
with aminoalkyl bis(o-aminophenol) ligands have been synthesized in one-pot and one-step by
mannich condensation reaction of Ni(o-aminophenol)2 complex, with formaldehyde and primary
amines (such as ethylamine, buthylamine, benzylamine) at room temperature in methanol solution
(2:2:1 mole ratio respectively). The imine intermediate can formed by reaction the Ni(oaminophenol)2 complex with formaldehyde, finally tetradentate nickel(II) complexes were formed
by react the imine intermediate with the primary amine. These complexes have been characterized
by elemental analyses and IR, UV-Vis spectroscopy. All complexes show similar IR and electronic
spectral features. The IR spectra the complexes prepared exhibited the characteristic bond around
1250-1280 cm-1 corresponding to υ(CN).
Keywords: Nickel(II) complexes, Tetradentate, Mannich reaction, o-aminophenol
P-476
Ag Nanoparticles Encapsulated on Ionic Liquid Matrix, Immobilized to ZnO NPs
Farnaz Movahedi, Hassan Masrouri and M.Z. Kassaee*
Surface modification of pristine magnetic nanoparticles is a frequently used method to promote the
performance of nanoparticles as drug carrier and bioseparator. Ionic liquids (ILs), novel class of
versatile solvents, have emerged and employed either as catalyst or promising homogeneous
catalysis media because of their unique physicochemical properties including negligible vapor
pressure, wide liquid range, high ionic conductivity, and excellent solubility. Herein, we report
synthesis of Ag@ZnO-ionic liquid nanoparticles as a novel and efficient catalyst. For this purpose,
ZnO nanoparticles were constructed, using chemical reduction method in which the average size
gained 23 nm. On the other hand, the desired ionic liquid (IL) means 1-(3-trimethoxysilylpropyl)-3methylimidazolium chloride {[tmim][Cl]} was produced. The mentioned ionic liquid chains were
immobilized to the surface of ZnO NPs, so led to the advancement of the catalytic properties as well
as benign environmentally. At the next stage, Ag NPs were synthesized from AgNO3 in the presence
of modified ZnO-IL NPs matrix, with average size of 6 nm. As a result the produced Ag NPs were
encapsulated and formed to the Ag@ZnO-IL NPs with catalytic potential used for organic reactions.
All the steps in construction the ultimate catalyst were verified with characterization analysis such
as XRD, ICP, TGA, SEM and TEM.
Keywords: Ag nanoparticles, Ionic liquid, ZnO nanoparticles, Chemical reduction
IICC12
271
P-477
Investigation of interaction of cobalt(III) complex containing modified phenanthroline
ligand with anionic surfactant
M.Aminzadeh, A.Eslami ̽
Faculty of Chemistry, university of Mazandaran, Babolsar, Iran̽
Dipyrido-[2,3 -a:2`,3`-c]-phenazine (DPPZ) ligand is one of 1,10-phenanthroline derivatives
Complexes of (DPPZ) Ligand and it`s analogues are much studied and employed in view of their
applications in several research Areas, including bioinorganic and biomedicinal chemistries. Series of
mixed ligand complexes of the type [Co(III) (LL) 2 X2]X (where LL= derivative of 1,10phenanthroline , X= alogen),as shown below, have been investigated. In this study an attempt is
made to gain more insight into the nature of interaction of this metal complex with biological
structure using simplest model for membrane, i.e. SDS (Sodium Dodecyl Sulfate) by Uv-Vis and RLS
(Resonance Light Scattering) spectroscopy. All compounds were characterized by UV-Vis, FT-IR,
NMR spectroscopies.
Keywords : DPPZ ,Cobalt(III) , RLS , phenanthroline , SDS
P-478
Investigation of Novel ZnO/MoO3 Nanocomposites by Using Organic–Inorganic layered
hybrids of Molybdenum Oxide
M. Movahedia,*, M. Afsharpourb and A. Hosseinianc
Department of Chemistry, Payame Noor University (PNU), Isfahan, Iran
Nano Science and Technology Research Center, University of Tehran, Tehran, Iran
c
Department of Engineering Science, Universities Colleges of Engineering,
University of Tehran, Tehran, Iran
a
b
The ZnO/MoO3 nanocomposites were synthesized by using MoO3 hybrids as a host of zinc oxide.
These organic–inorganic layered hybrids are used as a precursor for the organization of
nanostructured molybdenum oxide within a longer predefined space. These nanoplatelets would
allow a more efficient intercalation of zinc oxide into the layer of molybdenum oxide. The
nanostructures have been characterized by means of XRD, SEM, XRD and FTIR. The X-ray
diffraction results indicated that the as-synthesized powder has zincite ZnO, and orthorhombic MoO3
phases. Photocatalytic properties of the synthesized ZnO/MoO3 nanocomposites were tested for the
degradation of congo red azo dye. Among the various catalysts, these composites showed a high
efficiency towards the removal of congo red.
Keywords: Nanocomposite, Zinc oxide, Molybdenum oxide, Photocatalyst.
272
IICC12
P-479
The study of ring effects on 31P chemical shifts, coupling constants and IR stretching
frequencies on some new carbacylamidophosphates
a
S. Movasseghi a*, Kh. Gholivand b, Z. Hosseini b
(e-mail: sanam_390@ yahoo.com)
b
Research on compounds with RC(O)N(H)P(O) moiety are of interest based on their complexation
reactions and the inhibition of urease enzyme. In this work, we synthesized some new compounds
with formula CH2ClCHCH3C(O)NHP(O)(X)2, X= N(C2H5)2 (1); X= N(C3H7)2 (2); NC4H8 (3); NC5H10 (4)
and NC6H12 (5) and characterized by IR, multinuclear NMR spectroscopy and elemental analysis.
These compounds were synthesized according to the Scheme 1. Results showed in compounds (3)
and (4) with five and six-membered ring amine groups, 3J(P,C)>2J(P,C). In opposite to compounds
with five and six-membered ring amine groups, compounds containing acyclic aliphatic amines and
seven-membered ring amine, show 2J(P,C)>3J(P,C). Phosphorus chemical shifts in these compounds
are observed in the range of 6.37 to 12.15 ppm. Stretching vibrations of ν(P=O) and ν(C=O)
appeared in the range 1201-1232 cm_1 and 1630-1684 cm_1.
Keywords: Carbacyl amidophosphate, Coupling Constant, Spectroscopy, Ring effect.
P-480
Effects of Temperature, Reaction Time and Electrophyl on the Phosphorylation Reaction
of Methacrylamide
a
S. Movasseghi a*, Kh. Gholivand b, Z. Hosseini b, A. A. Kalatehb
(e-mail: sanam_390@ yahoo.com)
b
In recent years, investigations on N-Carbonyl phosphoramidates are an important part of
phosphorous chemistry due to their synthetic, structural, coordination and biological applications.
Herein, we have considered the synthesis and spectroscopic characterization of several new Ncarbonyl
phosphoramidates
with
formula
CH2CCH3C(O)NHP(O)(X)2,
X=Cl
(1);
CH2ClCHCH3C(O)NHP(O)(X)2, X= Cl (2), OH (3). Compound (1) was prepared according to the
Scheme 1. Changes in the reaction conditions afforded product (2), as by increasing the
temperature and reaction time, the double bond reduction of CH2C(CH3)- was obsereved. However,
the use of POCl3 as phosphorylating agent and decreasing the temperature and reaction time gave
product (3). The structure of compounds (1), (2) and (3) were caracterized by 1H, 13C, 31P NMR, IR
spectroscopy and CHN elemental analysis. It is interesting that two protons of CH2Cl- moiety in (2)
and (3) were diastrotopic and indicated two separate signals for the two non-equivalent H in 3.35
and 3.57 ppm and coupled with neigboring protons in pattern of dd. The results showed that
effects of the temperature, reaction time and electrophile on the phosphorylation reaction of
methacrylamide led to the formation of different products.
Keywords: N-Carbonyl phosphoramidate, Methacrylamide, Diastrotopic, Spectroscopy.
IICC12
273
P-481
Selective oxidation of alcohols to aldehydes using inorganic-organic hybrid catalyst
based on transition metal substituted polyoxometalate (TMSP) and ionic liquid (IL)
Z. Nadealian, V. Mirkhani*, B. Yadollahi
(E-mail: [email protected], E-mail: [email protected])
Polyoxometalates (POMs) are metal-oxo anionic clusters whose chemical properties can be
controlled by transition metal substitution and the type of countercation. Keggin structures,
[Xn+M12O40](8-n)-, (X: P5+, Si4+, Ge4+, B3+ and M: W6+ or Mo6+) are most investigated
polyoxometalates. The addenda atoms, M, can be substituted by other transition metals to form
transition metal substituted polyoxometalates (TMSP). TMSP compounds have been reported as
excellent catalysts in oxidation reactions. Ionic liquids are liquids comprised predominantly of ions
and ion-pairs at some given temperature. The properties of ionic liquids are including excellent
thermal stability, highly viscous, wide liquids regions and favorable solving properties for a range of
polar and non-polar compounds. Selective catalytic oxidation of alcohols to carbonyls is one of the
most important chemical transformations in industrial chemistry. Carbonyl compounds such as
ketones and aldehydes are the precursors for many drugs, vitamins, and fragrances and they are
also important intermediates for many complex syntheses. In the present study, the solid hybrid
compound [bmim]5[PW11ZnO39].3H2O ( bmim: 1-n-buthyl-3-methyl imidazolium), has been prepared
and characterized by elemental microanalysis, UV-vis, FTIR, 1H-NMR and TGA. The synthesized
hybrid compound was used as catalyst for the oxidation of various alcohols by hydrogen peroxide
as oxygen source and the effect of solvent, oxidant and temperature was investigated. Results
showed good to excellent catalytic activity and product selectivity.
Keywords: Hybrid catalyst, Polyoxometalates, Ionic liquids, Oxidation.
P-482
Synthesis and Characterization of Aluminium incorporated mesoporous KIT-6 and
Investigation of Catalytic Activity
E. Naderi, R. Fazaeli* and H. Aliyan
Since the ordered mesoporous silicas, KSW-1 and MCM-41, were reported firstly in the 1990s, many
other mesoporous silicas with various pore geometries, such as MCM-48, SBA-15, SBA-16, KIT-6
and FDU-12, have been synthesized and characterized chiefly by low-angle powder X-ray diffraction
(XRD), transmission electron microscopy (TEM) and N2 adsorption/desorption. Among the
mesoporous materials, KIT-6 exhibits a three-dimentional cubic Ia3d symmetric structure with
interpenetrating bicontinuous network of channels. In order to improve the catalytic activity of this
material, one must incorporate heteroatom into the framework either by grafting or direct
synthesis. We report the successful incorporation of aluminium into the mesoporous KIT-6 with high
structural regularity under low acidic conditions and report a suitable method for the use of Al-KIT-6
as catalyst for the aerobic oxidation of alcohols.
Keywords: Nanoparticles, mesoporous solids, Polyoxometalates (POMs).
274
IICC12
P-483
Catalytic Sulfides Oxidation by Vanadium(IV) and Vanadium(V)-tetradentate Schiff
base Ligand using UHP as Oxidant
S. Nadiri , M. Bagherzadeh*
*
e-mail: [email protected] (M. Bagherzadeh)
The selective oxidation of sulfides to sulfoxides is an important method in organic synthesis because
sulfoxides are useful synthetic intermediates for the construction of various chemically and
biologically significant molecules. A variety of oxovanadium (IV) complexes have been shown to
catalyze the oxidation of sulfides. Oxovanadium (IV)(salen) and oxo Vanadium(V)(salen)Cl were
synthesised and screened in the vanadium-catalyzed oxidation of sulfides to solfuxides with urea
hydrogen peroxide(UHP) as terminal oxidant. Full characterization of these complexes was
accomplished with spectroscopic studies (NMR, IR and UV-VIS). Both complexes show good activity
and selectivity to sulfoxide formation in the catalytic reaction. Oxidation of sulfides to sulfoxides by
this catalyst using urea hydrogenperoxide (UHP) were carried out in mixture of
methanol:dichloromethane (1:1) under mild condition. The effect of the reaction conditions on the
oxidation of methylphenylsulfide was studied by varying the amount of the catalyst, reaction time
and the amount of UHP. Catalysts are successfully applied in the selective oxidation of various
sulfides to sulfoxides with 94–100% yield and 75–100% selectivity.
Keywords: Schiff bases -urea hydrogen peroxide - selective sulfoxidation-sulfide-catalytic
oxidation
P-484
Synthesis and Spectroscopic Characterization of Two New Phosphorylamidates, Crystal
Structure of [(C6H4(3-CH3)NH)]9[P(O)]3(C2H5O)3
M. Negari*, H. Eshtiagh-Hosseini, M. Pourayoubi
Phosphoramidates are an important class of compounds due to their different applications in
medicine, pharmacology, agriculture and coordination chemistry. Some new phosphorus
compounds with formula [(C6H4(3-CH3)NH)]9[P(O)]3(C2H5O)3 (1), [(C6H5O)2P(O)(NHC6H11)] (2), has
been synthesized and characterized by 1H, 13C and 31P{1H} NMR, IR. Moreover single crystal X-ray
diffraction was performed for compound 1. Single crystal X-ray analysis shows that it belongs to
triclinic system, space group P-1, with a = 12.5401(11) Å, b = 12.8961(7) Å, c = 23.8258(10) Å, α
= 92.411(4), β = 101.934(5), γ = 114.075(6), Z = 6. The crystal lattice of compound 1 contains
three crystallographically independent phosphoramidate molecules as well as three hydrogenbonded C2H5OH molecules with slightly differences in the bond lengths, angles and torsion angles.
The O-H…O and N-H…O hydrogen bonds are responsible for the extended chain aggregation in
crystal network.
Keywords: Phosphoramidate, crystal structure, X-Ray Crytallography.
IICC12
275
P-485
Some New Heterodinuclear Lanthanide Complexes (Ln=La, Tb, Pr): Synthesis and
Luminescence Properties
M. Negari*, M. Pourayoubi, H. Eshtiagh-Hosseini
Lanthanides have a complex electronic configuration due to the existence of 4f, 5d and 6s orbitals.
Stabilization of these orbitals favors the 4fn open-shell oxidation states of +3 for most lanthanides.
Excitation of 4f electrons and subsequent relaxation generates the spectroscopic properties which
have made lanthanide complexes attractive for such a wide variety of application. Recently fblock/d-block bimetallic complexes have attracted attention and their role as building blocks for
polymeric materials is a significant field of study in recent years. In this research, the reaction of
LnCl3.xH2O (Ln = La, Tb, Pr) with NH4[Cr(SCN)4(NH3)2] in DMF and ethanol were studied and the
crystalline products were investigated by IR, NMR, UV-visible and fluorescence spectroscopy. The
design goal for the d-block/f-block mixed metal complexes is to use the lower energy metal to
ligand charge transfer (MLCT) transitions associated with the d-block metal to induce the lanthanide
4f–4f emission.
Keywords: Heterodinuclear, Lanthanide complex, metal to ligand charge transfer, f-block/d-block.
P-486
Facile Fabrication of Nanosized Ferrites
A. Naghdi Sedeh and M. Kooti*
Many studies have been focused in recent years on the synthesis of metal oxide nanoparticles
because of their unusual optical, electrical and magnetic properties. Ferrites which have the general
formula of MFe2O4 (M = Mn, Co, Zn, Mg, etc.) with spinel structure are a family of oxides having
great technological importance because of their novel physical properties. The basis for the wide
range of applications is related to the variety of transition metal cations that can be incorporated
into the lattice of the parent magnetite structure. In the fabrication of these ferrites the shape and
size of the nanopartcles have to be controlled because these factors have important effects on the
physical and chemical properties of the produced ferrites. Here we report a simple and fast route
for the preparation of a variety nanoscale MFe2O4 ferrites (M = Fe, Zn, Mn,…) using metal glycine
precursors. Heating a mixture of appropriate salts of the metals with glycine by microwave afforded
the ferrites nanoparticles with high yield and purity. The reactions took place at solid phase and the
products were isolated merely by washing with water and some organic solvents. No heat
treatments are required in our procedure of making these ferrites. The as-prepared ferrites were
characterized by various techniques such as, FT-IR, XRD and TEM. The magnetic properties of the
synthesized nanonocrystals ferrites were studied and compared with the previously synthesized
ones. The effect of the presence of PEG, as size controlling reagent, on the size and property of
some of these ferrites was also investigated.
Keywords: Nanoparticles, Ferrites, Microwave, Glycine, TEM
276
IICC12
P-487
Microwave-assisted synthesis of nanosized Iron (III) oxides
A. Naghdi Sedeh and M. Kooti*
In this study, we have adapted microwave-assisted route to prepare α-Fe2O3 and γ-Fe2O3
nanoparticles using glycine iron (III) precursor. In this method, Iron (III) nitrate was mixed with
glycine (1:3 molar ratios) in the presence of PEG or without PEG and the mix was heated in a
microwave for a short time to produce γ -Fe2O3 (maghemite) and α -Fe2O3 (hematite) respectively in
quantitative yields. The prepared iron oxides were of pure samples and there was no sign of
magnetite (Fe3O4) formation or starting materials. The as-prepared maghemite and hematite
nanoparticles were characterized by various techniques including FTIR, X-ray powder diffraction
(XRD) analysis, scanning electron microscopy (SEM) and transmission electron microscopy
(TEM).Our procedure for the fabrication of two of the important iron oxides nanoparticles is simple
and used materials are inexpensive. Therefore, it can be introduced as a very economic,
environmentally-friendly, simple, fast and reproducible method for synthesizing of γ -Fe2O3 and α Fe2O3 nanopowders. This method was extended to the synthesis of other nanosized transition metal
oxides, such as CuO, Co3O4 and NiO. These metal oxides which have many important applications
were successfully prepared by the procedure of decomposing of their metal glycine precursors. The
effect of various factors, such as other amino acids, on the size and quality of the fabricated metal
oxides nanopartcles is also under investigation.
Keywords: Maghemite, Hematite, Nanopartcles, Microwave-assisted
P-488
Efficient Synthesis of 2-arylimidazoles by Oxidation of 2-arylimidazolines with Sodium
Periodate Catalyzed by Mn(TPP)Cl Supported on Polystyrene-bound Imidazole
a
M. Naghipoura, H. Kargar*,a, V. Mirkhanib
Department of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
b
Substituted imidazoles are important moieties constituted in pharmaceuticals, pesticides and
bioactive compounds. There have been many reports for the synthesis of imidazole derivatives.
Among those, oxidative conversion of imidazoline to imidazole is a general and reliable method.
Actually, KMnO4, MnO2, BaSO4, Pd/C, trichloroisocyanuric acid (TCCA) and o-iodoxybenzoic acid
(IBX) have been used as oxidizing agents. Here, we report an efficient oxidative synthesis of 2substituted imidazoles from the corresponding imidazolines with sodium periodate catalyzed by
Mn(TPP)Cl supported on polystyrene-bound imidazole. The prepared catalyst was used for the
oxidation of 2-arylimidazolines with sodium periodate at room temperature. First, reaction
parameters such as catalyst amount and kind of solvent were optimized in the oxidation of 2phenylimidazoline and the NaIO4 and acetonitrile: water was chosen as oxidant and reaction media,
respectively. The catalyst was reused several times without loss of its activity.
Keywords: Imidazoline, Imidazole, Periodate, Supported metalloporphyrin, Polystyrene
IICC12
277
P-489
Catalytic oxidation of olefins with hydrogen peroxide in the presence of dissymmetric
Schiff base manganese and cobalt complexes
Saideh Nahavandi and Hassan Hosseini Monfared *
Department of Chemistry, Zanjan University 45195 -313, Zanjan , Iran
(e-mail: [email protected]; [email protected])
Six complexes of cobalt(II) and manganese(II) with the in-situ formed tridentate hydrazone Schiff
base ligands HL1 (benzoic acid (2-hydroxy-3-methoxy-benzylidene)-hydrazide, HL2 (benzoic acid (2hydroxy-benzylidene)-hydrazide) and HL3 (benzoic acid (5-bromo-2-hydroxy-benzylidene)hydrazide) were synthesized. These complexes were prepared by addition of an ethanolic solution
of benzhydrazide to ethanolic solution of appropriate salicylaldehyde and MnCl2.4H2O/CoCl2.6H2O
solution to yield [MnΙΙCl(L1)(H2O)2], [MnΙΙCl(L2)], [MnΙΙCl(L3)], [CoΙΙl(L1)2H2O, [CoΙΙ L2 (Cl)], and [Co2ΙΙ
(L3)2(H2O)2]. The complexes were characterized on the basis of their FT-IR and elemental analyses.
Catalytic ability of the M-L1-3 (M = MnII, CoII) complexes were examined in the oxidation of
cyclohexene and cyclooctene with aqueous 35% hydrogen peroxide. Effects of temperature,
catalyst nature, oxidant concentration, co-catalyst, and co-solvent in catalytic oxidation of olefins
were studied. It was found that cobalt catalysts were active than manganese complexes and
maximum conversion of cyclooctene was obtained with Co-L1/Imidazol/H2O2/CH3CN system at 60
0
C. The only product of the cyclooctene oxidation by this system was cyclooctene epoxide.
Keywords: Catalysis, Cobalt, Manganese, Hydrogen peroxide, Oxidation, Olefin.
P-490
Synthesis and Characterization of a Related Series of Dihaloplatinum(II) Complexes
Containing Chelating Phosphine Ligands: Effect of the Tin(II) Halide in the Pt-Sn
Products
Badri Z. Momeni*, Atefeh Najafi
Department of Chemistry, K. N. Toosi University of Technology, Tehran, Iran
Few synthetic studies have been devoted to date in the case of the binary complexes of Pt/Sn
containing mixed halides and their chemistry has not been investigated in detail. Therefore, we
became interested to investigate the reactions of SnX2 (X=Cl, Br, I) with dihaloplatinum(II)
complexes containing a related series of chelating phosphine ligands. The insertion of SnI2 into Pt-I
bond could not be observed for a related series of diiodoplatinum(II) complexes containing
chelating phosphine ligand, however, the insertion of SnCl2 into Pt-I bond was observed only in the
case of cis- [PtI2(dppm)] (dppm = bis(diphenylphosphino)methane). The selective halogen
exchange in the presence of tin(II) halide in the seven-membered ring will be discussed. This
presentation will also discuss the synthesis of the complexes of the type [PtX2(P2)] (X = Br, I) and
their 31P NMR data are reported. These compounds were examined by NMR spectroscopy and
therefore, comparison with the results from the reactions of the complexes cis- [PtCl2(P2)] with SnX2
(X= Br, I) makes it possible to assign the stereochemistry of complex in each case. It will be
shown that the treatment of the tin(II) halide with dihaloplatinum(II) complexes containing
phosphine ligands can be influenced on the formation of the oligomers containing bridging group of
phosphine ligand as well as cis-trans isomerization.
Keywords: Platinum, Tin, Insertion, Chelate, Spectroscopy
278
IICC12
P-491
Investigation of aggregate [SbW9O33]9- Polyoxometalate by cerium ion linkage
N. Najafia, F. Mohammadi Zonozb,*, S. Tavakolia and H. Salahshoorniaa
a
b
Sabzevar Tarbiat Moallem University, Sabzevar, Iran
The use of polyoxometalates as basic building blocks to construct novel extended materials by
means of different cationic linkers is of great interest and stems not only from their intriguing
variety of architectures and topologies, but also from their numerous potential applications in
catalysis, sorption, magnetic materials, and bioinorganic pharmaceuticals. In this field, lanthanide
cations are popular linkers due to their high coordination numbers and oxyphilic activities. Lacunary
polyoxometalates can be obtained by the removal of one or several metal centers under the special
pH value of solutions, in which the Ln atoms occupy the vacant sites of the polyoxoanions.
Derivatives of lacunary polyoxometalates in which more than one metal atom has been lost, for
example, the XM9O33n- complexes present a rang of structures and potential applications. This
research was done in possibility of incorporated Ce ions in trivacant specie of the [SbW9O33]9- results
in the formation of complexes like (SbW9)2Ce2 In this work, Na12[Sb2W18Ce2O66].42H2O have been
successfully synthesized and the existence of Ce ion characterized with elemental analysis, IR
spectroscopy, cyclic voltammetry (CV) and pulse differential polarography. Unlike our expectation,
only two Ce ions incorporate between polyoxometalate units, instead of three Ce ions that it is not
unusual. Such as Sb2W20M2O70(H2O)6 and NH4As2W18U2O72.
Keywords: Polyoxometalates, Lanthanide, Cerium ion, Lacunary polyoxometalates, Polyoxoanions.
P-492
Hydrogen bond controlled out-of-plane deformation of porphyrin core induced by weak
carboxylic acids: UV-vis and electrochemical studies
a
M. Najafi Ragheba, S. Zakavia,*, M. Rafieea
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan, Iran
Nonplanar distortions of tetrapyrroles are prevalent in the hemes of hemoproteins, the pigments of
photosynthetic proteins, and cofactor F430 of methylreductase. The nonplanarity of these porphyrin
cofactors is currently believed to influence factors in the biological activity of the proteins, in part,
because the porphyrin deformations are often conserved within functional classes of proteins.The
origin of the red shifts seen in the optical spectra of non-planar porphyrins has generated
considerable controversy in the literature. We have recently reported the interaction of mesotetraaryl- and meso-tetra(n-propyl)porphyrins with weak and strong carboxylic acids. However, little
has been known about the adducts formed between the weak carboxylic acids and porphyrins. In
the present work, cyclic voltammetry data in combination with UV-Vis one have been used to
explain the change in the porphyrin frontier orbitals as well as the out-of-plane deformation of the
macrocycle upon adduct formation between meso-tetra(para-tolyl)porphyrin and weak carboxylic
acids. The results of this study suggest that the origin of UV-vis spectral shifts accompanied with
the adduct formation of porphyrins with weak carboxylic acids is significantly different from that in
the case of diprotonation of porphyrins with strong acids.
Keywords: Hydrogen bond, Adduct formation, Out-of-plane deformation, Porphyrin.
IICC12
279
P-493
Toxicity effects of vanadium complexes on iron blood and regeneration in male rats
F. Najafizadeh∗ 1, A. Amiri 2, Sh.fouladi 3
Department of Chemistry, Islamic Azad University kerman Branch, Kerman , Iran.
(e-mail:najafizaded_ ir @yahoo.com)
2
Department of Chemistry , Vali-e-asr University , Rafsanjan , Iran.
3
Educated of Biochemistry Department, Payame Noor University (PNU), Tehran. Iran
1
In human body 4g iron exists that 70% of this is in the hemoglobine and others are in some
proteins and enzymes. Transferin is one of the proteins that solve Fe3+ in blood. In our blood
transferin can saturated about 30% by Fe3+ so there is a capacity for bonding of transferin by other
metal ions that enter our body by different ways. Accordingly toxic environment causes venenation,
anemia and sterility. We probe a way that solves the problem of people who live in toxic
environments as industrial regions. At first experimental rats were fed vanadium (III) at dose of
50mg/kg for a month. At the end of this time chelation therapy was done by using L1 (Deferiprone)
+DFO (Desferrioxamine) and L1+ DSF (Desfonak) for a week. In all of the procedures a control
group was used that were Fed by water and standard Food. We killed rats by Co2 and sampled from
blood and epididim of them. We measured the quantity of iron in blood with atomic absorption
spectroscopy method and the numbers of spermatozoones were measured by the method of Besly.
The results are satisfactory because after treatment anemia decreased and the number of
spermatozoones increased. Of course the effect of treatment by L1+ DSF is better than L1+DFo.
Keywords: Toxicity, Vanadium complexes, Iron, Spermatozoon, Rat
P-494
Interaction of 3-(3,4-dihydroxybenzylidene)-7-methoxychroman-4-one and 3-(3,4dihydroxybenzylidene) -7-propoxychroman-4-one with RNA
Narjes Namdar baboli , F.Manouchehri , T.Sadigh Vishkaee , N.Makouie , Sh.Nafisi*
Department of Chemistry, Islamic Azad University, Central Tehran Branch, Tehran, Iran
[email protected]
Flavonoids are a class of natural polyphenolic compounds,which are recognized as a secondary
metabolites in the plant and has a important role in the defense against free radicals. These
compounds show antiviral, antibacterial, anti-inflammatory properties, and preventing role in
cancer, Alzheimer's, Parkinson's and cardiovascular diseases. This study was designed to examine
the interactions of one of the most important kinds of antioxidants, called 3-(3,4dihydroxybenzylidene)-7-methoxychroman-4-one
and
3-(3,4-dihydroxybenzylidene)-7propoxychroman-4-one with calf thymus RNA in aqueous solution at physiological conditions, using
constant RNA concentration (0.51mM)and various concentration of drug. UV-visible spectroscopic
method have used to determine binding constant and the stability of RNA in 3-(3,4dihydroxybenzylidene)-7-methoxychroman-4-one
and
3-(3,4-dihydroxybenzylidene)-7propoxychroman-4-one—RNA complexes in aqueous solution. spectroscopic evidence showed major
binding of 3-(3,4-dihydroxybenzylidene)-7-propoxychroman-4-one to RNA with overall binding
constant of K=1.55×104 M-1 and weaker binding of 3-(3,4- dihydroxybenzylidene)-7methoxychroman-4-one to RNA with overall binding constant of K=1.08×104 M-1(where K is the
binding constant)
Keywords: RNA, Flavonoids, Methoxychroman, Propoxychroman, Binding Constant , UV-visible
spectroscopy
280
IICC12
P-495
Oxidation of 2-substituted Imidazolines to Corresponding Imidazoles with Sodium
Periodate Catalyzed by Mn(Br8TPP)Cl
a
I. Namenia, H. Kargar*,a, M. Moghadamb
Department of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
b
Metalloporphyrins are versatile oxidation catalysts which have been used as models for
monooxygenases based cytochrome P-450. The most efficient systems involve iron and manganese
tetraarylporphyrins bearing electron-withdrawing substituents on the aryl group. Imidazole
derivatives are chemically and pharmaceutically important compounds. Recently, imidazoles have
been found to be attractive as a skeleton of ionic liquids in many fields such as environmentally
friendly solvents in organic synthesis, electrolytes, and liquid crystals. The oxidative of imidazolines
is a general and reliable method for synthesis of 2-substituted imidazoles. In this work, we report a
new approach for oxidation of 2-substituted imidazolines to their corresponding imidazoles with
sodium periodate catalyzed by Mn(Br8TPP)Cl.The prepared catalyst was used for the oxidation 2substituted imidazolines with sodium periodate at room temperature. The kind of solvent and
amount of catalyst were optimized in the oxidation of 2-phenylimidazoline. The catalyst was reused
several times without loss of its activity.
Keywords: Imidazoline, Imidazole, Periodate, Octabromotetraphenylporphyrine.
P-496
Synthesis and Identification of Two Novels Isostructure ‘Base Carboxylate’Complexes
Cr3O and Fe3O with Thiourea
M. Naseha,*, V. Amanib, M. Afsharic and A. Zareia
Department of Chemistry, Islamic Azad University, Dezfoul Branch, Iran
b
Department of Chemistry, Islamic Azad University, Shooshtar Branch, Iran
a
c
Polynuclear transition metal complexes occur widely in nature, and their study span fields ranging
from biology to physics. The triangular ensemble of the metal ions with the central oxo bridge is
stabilized by various carboxylate (RCO2-) and different neutral mono dentate ancillary ligands (L).
General formula for these compounds is [M3O(O2CR)6L3].nS where M is metal atom, L is terminal
mono dentate ligand, and S is solvent molecule of crystallization. Three metal atoms are bridged by
the oxygen atom located at the center of the three angles of metals and also by the six carboxilate
ligands in the circumference. In this paper, we synthesize two cluster compounds
[Cr3O(OAc)6(Thiourea)3]Cl and [Fe3O(OAc)6(Thiourea)3]Cl with exchange the monodentate ligand
(L) with thiourea and prove that with IR spectra and elemental analysis.
Keywords: Chromium, Iron, Synthesis, Infrared, Band Assignment.
IICC12
281
P-497
Organotin(IV) Complexes Involving Sulfur-Nitrogen Donor Ligands with Competitive
Reactive Centers: ab initio Studies
M. Naseh, T. Sedaghat*, A. Tarassoli, E. Shakerzadeh
Chemistry Department, Shahid Chamran University, Ahvaz, Iran
Organotin(IV) complexes present an interesting variety of structural possibilities, so that remarkable
diversity in structure may be observed even when only a small change in the chemistry occurs. 2Amino-1-Cyclopentene-1-carbodithioic acid (H2ACDA) and its derivatives are versatile chelating
agents with dual capability of coordination (S,S:1 or N,S:2). We have reported earlier synthesis and
structure of diphenyltin(IV) complexes with H2ACDA and N-alkyl derivatives. It is shown
experimentally that in all cases disulfur chelation occur. In this study, the considered compounds,
which are depicted in Scheme, are optimized at HF level of theory and different basis sets (3-21G*,
SDD for Sn atom and 6-31G* for others, LANL2DZ for Sn atom and 6-31G* for others) using
GAUSSIAN 98W. Some quantum mechanical principles such as Maximum Hardness Principle (MHP)
and Minimum Electrophilicity Principle (MEP) are used to predict the stable compounds (i.e. S,S
bonding mode). It is clear from Table that MEP successfully predict (S,S) bonding mode, which X–
ray crystallography emphasis the accuracy of these results. In all cases the stable compounds have
less electrophilicity values with respect to the S,N bonding mode.
Keywords: Organotin, Dithiolate, ab initio, Chelation
P-498
Synthesis and Characterization of New Schiff base Complexes from tetradentate Ligand
(N4) in the Presence of Zn2+, Cu2+ ,Cd2+, Mn2+, Ni2+
a
H. Goudarziafshar*, a M. Nikoorazm, a A.Ghorbani Choghamarani, b H.keypour and Zahra Naserifar
a
b
Faculty of Chemistry, University of Bu-Ali- Sina , Hammadan,Iran
Schiff base complexes of transition metals could be applied in different areas such as
electrochemistry, pharmaceutical, bioorganic, catalysis, metallic deactivators, separation processes,
and environment chemistry among others. Study of polyamine complexes has contributed in large
measure to the rationalization of coordination compound formation polyamines form stable
complexes both in aqueous solution and in the solid state for example, almost all the metals of the
3d transition series form homogeneous series of polyamine complexes. In recent years, tripodal
ligands have been of interest, and many combinations of donor sets have been assembled. In this
work, we prepared a new tetradentate ligand (N4) Schiff base macroacyclic complexes [ML]2+
(Figure1) from reaction of N, N’- bis (2-amino ethyl) propan-1,3- diamine L1 that it was synthesized
by previously methods, and 9-anthraldehyde aldehyd L2 in presence of M2+( Zn2+, Cu+2) as a insitu
synthysis. These complexes were characterized by various spectroscopic methods (IR, Mass,1
HNMR, 13CNMR)
Keywords: Schiff base, Tetradentate, Macroacyclic, Ttripodal ligand, Insitu synthysis
282
IICC12
P-499
Application of an organo-metallic compound as a mediator for determination of sulfite
using multi-wall carbon nanotubes paste electrode
Vahid Nasiri-Ghadi, Mohammad A. Khalilzadeh*, Hassan Karimi-Maleh
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Iran
Carbon nanotubes are a new kind of inorganic material with nanostructure, which is promising as
an immobilization substance for different electron transfer mediators. The application of carbon
nanotubes for fabrication of electrochemical sensors and biosensors is reviewed by many research
groups. The electronic properties of these nanomaterials have been exploited as a mean of
promoting the electron transfer reaction for a wide range of molecules and biological species. In
this study, we describe application of an organo-metallic compound (ferrocene in this case) as a
new mediator for catalytic determination of sulfite in aqueous buffer solution (pH 7.0). Result shows
that under the optimum condition (pH 7.0) in cyclic voltammetry, the oxidation of sulfite is occurred
at a potential about 280 mV less positive than that an unmodified carbon nanotubes paste
electrode. Kinetic parameters such as electron transfer coefficient, (α) and heterogeneous rate
constant, (kh) for sulfite were also determined using electrochemical approaches. Under the
optimized conditions, the electrocatalytic oxidation peak current of sulfite showed a linear dynamic
range with a detection limit of 0.5 µmol L-1 sulfite. The proposed method was examined as a
selective, simple and precise method for voltammetric determination of sulfite in real samples such
as weak liquor from the wood and paper industry and boiler water.
Keywords: Sulfite, Multi-wall carbon nanotubes paste electrode, Ferrocene, Voltammetry, Weak
liquor
P-500
Study of complexation between naphen and naphpn as two new Schiff bases and some
metal ions in DMF by spectrophotometric method
a
S. Nasiri a, A. Shokrollahi b*, M. Montazerozohoori b
Department of Chemistry, Islamic Azad University of Firouzabad, Firouzabad 74715-117, Iran
b
Department of Chemistry, University of yasouj, Yasouj 75918-74831, Iran
Naphthaldehyde based Schiff bases is a new class of these compounds with high hydrophobic
property. It considers, which these Schiff bases can be proper ionophore to design the sensitive and
selective methods for determination of metal ions. In this work we studied the complexation of two
new derivatives of these class of Schiff bases including naphen and naphpn with some metal ions
such as Ni2+, Zn2+… in DMF solvent, at 25 ˚C and 0.05 M tetraethyl ammonium perchlorate (TEAP)
spectrophotometrically, at first time. Stoichiometry and stepwise stability constants of the obtained
complexes have been evaluated by computer refinement of Abs-mole ratio value at λmax of complex
or ligand, using the KINFIT program. The structurally effects of ligands on stability of complexes
were investigated.
Keywords: Spectrophotometric method, Naphtaldehyde based Schiff bases
IICC12
283
P-501
synthesis, characterization and properties of new nano halo aluminates
S. Nasiria, S.Ghammamya,b, A.Pourahmadc, M. Nasirtabrizia
Department of chemistry, Islamic Azad university, Ardabile Branch, Ardabil, Iran
b:
Department of chemistry, Faculty of science, Imam Khomeini International University, Qazvin,
Iran
c:
Department of chemistry, Faculty of science, Islamic Azad university, Rasht Branch, Rasht, Iran
a:
Aluminates were used in many industries such as ceramics, artificial jams, lasers, batteries, cement
chemistry, mineralogy and so on. New aluminate compounds found different and more special
applications such as ionic liquids for mobile Batteries. For this reason research on synthesis of new
aluminates has been increased and extended in recent years. In these research new type of halo
aluminates were synthesized, and characterized by spectroscopic methods. These new compounds
changed to nano scale by irradiation technique. Some properties of them such as biological that
contain anticancer and antibacterial of them were been studied. The general production formula is:
AlCl3 + MX
M[AlCl3X]
Key words: Aluminate compounds, Synthesis, Ionic liquids, Nano scale, Anticancer, Antibacterial
P-502
Water-Soluble Fe3O4-Aminoclay Nanoparticles
Hasan Nasrabadi, S. Jafar Hoseini*
[email protected]
Magnetic nanoparticles of iron oxide (Fe3O4) and its suspensions have extensive applications in
magnetic storage media, biosensing applications, medical applications, such as targeted drug
delivery, contrast agents in magnetic resonance imaging (MRI). Generally, magnetic iron oxide
nanoparticles can be prepared by co-precipitating ferrous and ferric ions in aqueous solution. The
magnetic nanoparticles obtained exhibit poor solubility or dispersibility. Recently, Nanoparticles of
Fe3O4 solubilized in non-polar solvents by functionalizing with hexadecyltrimethoxysilane (HDTMS).
Herein, we demonstrated the possibility of producing water-soluble Fe3O4 nanoparticles by using of
aminoclay as the water dispersible support. Aminoclay is a water-soluble Mg-phyllo(organo)silicates
containing pendant amino groups with the approximate composition R8Si8Mg6O16(OH)4, where R =
CH2CH2NH2. Fe3O4 nanoparticles were synthesized by co-precipitation method. Immobilization and
solubilization were performed by sonication of a mixture of Fe3O4 and aminoclay in water. Samples
were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and IR
spectroscopy. In summary, we have presented a simple route to synthesize water-soluble Fe3O4
nanoparticles by employing of aminoclay.
Keywords: Iron, Fe3O4, Nanoparticles, Water-Soluble, Aminoclay
284
IICC12
P-503
Synthesis and Characterization of ZnO/MCM-41 Nanocomposite and its Photocatalytic
Activity
M. nasrolahzadeha, M. Arab Chamjangalia, Gh. Bagheriana, B. Fahimi Rada, M.H. Loghmanib
a
Department of Analytical Chemistry, University of shahrood, shahrood, Iran
b
Extensive research is currently underway to develop supported photocatalysts for their good activity
in pollutants and dyes degradation. Because of organic functional groups interactions with surface
of mesoporous materials, supporting CuO as a photocalyst is a unique route for increasing
photocatalytic performance. CuO particles have decorated on the surface of MCM-41 by
ultrasonication cupric nitrate and NaOH during direct precipitation method followed by the
calcination. The textural and structural properties of CuO/MCM-41 are compared with those of pure
MCM-41. The crystal structure was characterized by X-ray diffraction (XRD). The morphology and
particle size were analyzed using a transmission electron microscopy (TEM). The photocatalytic
activity was tested on the degradation of methyl orange (MO). The experimental parameters such
as initial concentration of MO, catalyst loading, pH and the influence of the presence of H2O2 were
optimized for maximum degradation efficiency.
Keywords: Nanocomposite, CuO, MCM-41, Degradation, Methyl orange
P-504
Density Functional calculations on cobalt catalysts used in Fischer-Tropsch process
M. Nazari, A. Nakhaei Pour,*
Research Institute of Petroleum Industry, Gas Research Division, Tehran, Iran
The Fischer–Tropsch process (FT) is a set of chemical reactions that convert a mixture of carbon
monoxide and hydrogen into liquid hydrocarbons. A variety of catalysts can be used for the Fischer–
Tropsch process, but the most common are the transition metals cobalt, iron, and ruthenium. Nickel
can also be used, but tends to favor methane formation. Modern density functional theory (DFT)
calculations have been most often used for Fischer-Tropsch catalysts. The modeling gives
information about the elementary steps of FT synthesis on cobalt catalysts, such as adsorption,
desorption, bond cleavage, surface reactions, and hydrocarbon chain growth. Our goal is
performing DFT calculations on different phases of cobalt and investigating the effect of carbon
monoxide adsorption on it. Cobalt particles involved in FT synthesis typically contain several
thousands of cobalt atoms. The principal difficulty in modeling active sites of FT catalysts is the
uncertain structure of the catalyst surface. The catalytic supports are usually amorphous; a large
number of different surface species and phases can coexist simultaneously. The second difficulty is
due to computing. DFT methods are still computationally demanding, especially for catalytic
systems involving a lot of atoms of transition metals. Despite considerable progress in computing
methods, obtaining reasonable accuracy requires a high volume of numerical calculations.
Keywords: DFT calculations, cobalt catalysts, Fischer-Tropsch process.
IICC12
285
P-505
Synthesis of Ammonium Dinitramide (ADN) by Nitration of Potassium Sulfamate. The
Effect of Water and Temperature on Reaction Yield
M. Nazari, S. Ghadimi,*, S. M. Hosseini
Department of Chemistry, University of Imam Hossein, Theran, Iran
([email protected])
Nitration of potassium sulfamate was carried out using a mixture of sulfuric and nitric acid at -45˚C.
The reaction time was optimized at the mole ratio of sulfuric to nitric acid of (1:2:6). The
dinitramide salts are stable class of inorganic salts which can be used as oxidizer in solid
propellants. Dinitramidic acid is prepared by Nitration of a compound selected from a group
consisting of NH2NO2, NH4NH2CO2, NH2SO3H, NH(SO3H)2. Preparing dinitramide salts comprising
neutralization of Dinitramidic acid with a neutralizing agent e.g. ammonia. The effect of variation of
temperature was studied for the reaction carried out using a SA/NA (sulfuric acid / nitric acid) mole
2:6 for 1 mole potassium sulfamat at -65˚C, -55˚C, -45˚C.
Keywords: Ammonium dinitramide, Dinitramidic acid, potassium sulfamat
P-506
Selective oxidation of anilines catalyzed by Mn-substituted wells-dawson type
polyoxometalate
Maryam Nejaddehbashi, Bahram Yadollahi*, valiollah Mirkhani
*E-mail address: yadollahi@chem,ui.ac.ir
Particular attention is given to most developments of recent studies on the use of POMs as
heterogeneous and homogeneous catalysts for the selective oxidation and acid-catalyzed reactions
in various reactions since its catalytic features can be controlled at a molecular level. Tungstan–
POMs exhibit interesting catalytic properties, and has been proved to be useful catalysts for
oxidation of different substrates, such as amines. Over the last decade hydrogen peroxide has had
somewhat of a rebirth in its use as an oxidizing agent. H2O2 has an environmentally benign profile
since it decomposes to give only water and oxygen as the only reaction products, which makes it
one of the cleanest oxidant. The oxidation of amines is a fundamental reaction for the synthesis of
O-containing amine derivatives and both industry and academia have paid considerable attention to
them. Therefore, a variety of oxidation and catalytic methods have been investigated. In this work,
Mn-substituted wells-dawson type polyoxometalate synthesized and used for selective oxidation of
aromatic amines to the corresponding nitro derivatives.Various substituted aromatic amines were
converted to the corresponding nitrobenzenes by oxidation with aqueous. hydrogen peroxide. the
reaction was carried out at reflux and the products were obtained in very good to excellent yields.
Keywords: Catalysis; Oxidation; Hydrogen peroxide; wells-dawson polyoxometalate.
286
IICC12
P-507
Synthesis and X-ray crystal structure of low spin Fe(II) complex of an asymmetyric
tripodal Schiff base ligand
Amir ahmad Rezaei, Sadegh Salehzadeh,*
The most thoroughly studied tripodal compounds are the transition metal complexes of potentially
heptadantate Schiff base ligands derived from condensation of tren, tris(2-aminoethylamine), with
various suitable aldehydes. Previously we have reported the synthesis and characterization of a
number of metal complexes of potentially heptadentate(N7) tripodal Schiff base ligands. In this
work we report the synthesis and characterization of Fe(II) complex of a tripodal potentially
heptadentate(N7) tripodal Schiff base ligand. Firstly, (2-aminoethyl)bis(3-aminopropyl)amine (ppe)
was stirred with 2-formylpyridine in EtOH solution in the room temperature for about 30 minutes.
Then the Fe(ClO4)2·6H2O was added to above solution and mixture was stirred for 1 hour. The
resulting powder was collected and crystallized in methanol solution. The resulting deep violet
product, [FeL](ClO4)2, was characterized with IR, mass spectrometry, elemental analysis and X-ray
crystal structure determination. The results shows that all donor atoms of the potentially
heptadentate ligand, except the tertiary nitrogen atom, are coordinated to the central metal atom.
A theoretical study at DFT (B3LYP) level of theory confirms that the low spin iron(II) complex of L
has same structure at gas phase while the high spin iron(II) has a different structure in which the
tertiary nitrogen atom is coordinated to the iron atom.
P-508
Preparation and characterisation of Cu-Fe layered double hydroxides
K.Nejatia, * S.Davaria, Z.Rezvanib,M.Mansuorfara
Department of Chemistry, payam noor universityof Tabriz,Azarbijane sharghi, Iran
Department of chemistry, Azarbaijan University of Tabriat Moallem, Azarbijane sharghi, Iran
a
b
Layered double hydroxides (LDHs) are a typical of 2D compounds with layers of metal cations (M2+
and M3+) of similar ionic radii, which are coordinated by six oxygen atoms forming M2+/M3+(OH)6
octahedra. These octahedral form two-dimensional sheets via edge sharing and may stack together
with charge-balancing anions between the layers. These compounds find applications in different
fields, such as catalysis , water purification, biomedicine, etc. In this work we describe our attempts
to synthesize Cu-Fe-LDH was prepared by dropwise addition of mixed aqueous solution of Cu(NO3)2
and Fe(NO3)3 at constant pH of 8.5-9 followed by thermal treatment for 24h in the mixture of
water, 1-propanol and surfactant (Ethylene glycol)(volum ratio 0f 3:3:1). layered double hydroxides
with the hydrotalcite-like structure,containing Cu(II) and Fe(III) in the layeres , have been prepared
and caracterised by powder X-ray diffraction, FT-IR spectroscopy and scanning electron
microscope(SEM).All results are indicating that we obtained well-crystallized products with bidimensional structure compounds.
Keywords: Cu-Fe-LDH,XRD, FT-IR spectra ,SEM
IICC12
287
P-509
Study of acid herbicide removal by Cu-Al-NO3-LDH
K.Nejatia, * S.Davaria, Z.Rezvanib, M.Mansuorfara
Department of Chemistry, payam noor universityof Tabriz,Azarbijane sharghi, Iran
Department of chemistry, Azarbaijan University of Tabriat Moallem, Azarbijane sharghi, Iran
a
b
Cu-Al-NO3 Layered double hydroxide.is an anionic clay capable of removing anions from a solution.
Cu-Al-LDH were synthesized at constant pH followed by thermal treatment for 24h with different
solvent. layered double hydroxides with the hydrotalcite-like structure,containing Cu(II) and Al(III)
in the layeres , have been prepared and caracterised by powder X-ray diffraction, FT-IR
spectroscopy and scanning electron microscope(SEM). The aim of this work is to study the capacity
of Cu-Al-NO3-LDH to remove the acid herbicide 2,4-D(2,4-dichloro phenoxy acetic acid) from
aqueous solution, as well as investigate the in fluence of pH and temperature on the regeneration
process.Removal of the organic contaminants occurs mainly in first one hour. All results are
indicating that we obtained well-crystallized products with bi-dimensional structure compounds.
Keywords: Cu-Al-LDH, 2,4-dichloro phenoxy acetic aci,XRD, FT-IR spectra ,SEM
P-510
Synthesis and Chemistry of Tris (2-pyridyl) phosphine complexes of Mercury (II)
Bromide. X-ray Crystal Structure of [HgBr2 (PPh (2-py) 2)2]
A. Nemati Kharat* and A. Bakhoda
Pyridylphosphines are a convenient building block for the construction of transition metal
complexes. For many transition metals its preferentially binds through the nitrogen atoms of pyridyl
rings to form sandwich or half-sandwich complexes. Specially, PPh(2-py)2, P-monodentate
coordination mode are rare. The study of the coordination and structural chemistry of mercury(II)
halide complexes with ligands containing a variety of donor atoms has been a matter of interest
over several decades. Following Mann's seminal work in 1940, Mercury(II) halides are now known
to form a wide range of stoichiometrics with tertiary phosphine ligands. In this paper a novel
complex of HgBr2 with the previously decribed PPh(2-py)2 is reported.
Keywords: Pyridylphosphine; mercury(II) bromide; P(2-py)3; X-ray crystallography.
288
IICC12
P-511
Removal of Pb(II) from waste water using plant wastes modified by metal
nanoparticles
P. Nematollahia, H.R. Aghabozorgb,*, and M. Khosravia
Islamic Azad University, North Tehran Branch, Tehran, Iran
b
(e-mail: [email protected] , [email protected] )
a
Heavy metals are major pollutants in the environment due to their toxicity and threaten creatures
and human being at high concentrations. Lead is one of the three most toxic heavy metals. Typical
symptoms of lead poisoning are headaches, convulsions, chronic nephritis of the kidneys, brain
damage, central nervous-system disorders, etc.. Lead is widely used in many important industrial
applications, such as storage battery, manufacturing, etc.. In this study, the adsorption of lead(II)
onto treated Cousinia by H2O2/MgCl2, was investigated from aqueous solutions in the batch
biosorption experiments. Fresh Cousinia was collected from the hills of Tehran. The collected
Cousinia was washed for several times with distilled water and then air-dried in sunlight. The dried
Cousinia was sieved to particles of 1mm. The cousinia samples were modified using H2O2 and MgCl2
nanoparticles. The morphology of the modified samples was studied by scanning electron
microscopy (SEM). The biosorption study of the prepared samples, were performed at room
temperature using a Pb(II) pollution. The removal of Pb(II) from the solution was determined by
atomic absorption spectroscopy. The results showed that more than 96% of Lead ions were
removed by modified Cousinia from the solution.
Keywords: Heavy metals, Plant waste, Cousinia, Lead, Waste water
P-512
Preparation and characterization of dithizone coated Fe3O4 nanoparticles and the
effects for removal of the Cd+2 ions from aqueous media
Z. Niazzadeh-Najafia, M. Shakibaieb,c, K. Abdid ,M.Yousefia, A.R. Shahverdib,*
Azad University, Shahre-rey branch, Tehran, Iran ([email protected])
b
Department of Pharmaceutical Biotechnology and Pharmaceutical Sciences Research Centre,
Faculty of Pharmacy, Tehran University of Medical Sciences.
c
Department of Pharmaceutical Biotechnology, Faculty of Pharmacy, Kerman University of Medical
Sciences, Kerman, Iran.
d
Department of Medicinal Chemistry, Faculty of Pharmacy, Tehran University of Medical sciences.
a
In this investigation, magnetic cores (Fe3O4) nanoparticles were prepared by alkalization of aqueous
medium containing ferrous sulphate and ferric chloride. The TEM micrograph of nanoparticles
showed size ranging from 2.5-21 nm. In the next step, Fe3O4 nanoparticles were coated by
dithizone as an organic chelating agent and were characterized by different devices. Subsequently
coated nanoparticles were used for preconcentration and separation of trace amount of the
cadmium (Cd+2). The magnetic nanoparticles were removed by using an external magnetic field and
the remnant Cd+2 in aqueous media were measured by Flame atomic absorption spectrometry.
Various factors such as pH, temperature, sample volume and eluting agents were investigated to
identify the optimum condition for facilitating removal of the Cd+2 as a toxic and hazardous metal
ion. Our result showed that the highest removal of Cd+2 by magnetic nanoparticles take place at
pH= 8 and 60ºC.
Key words: Fe3O4, Magnetic nanoparticles, Dithizone, Flame atomic absorption spectrometry,
Cadmium
IICC12
289
P-513
Synthesis and characterization of Fe3+and Co2+ and Cr3+ complexes of tridentate
monocondensed Schiff bases and pyridine
E.Nikjooa , B.Shaabanib,*, S.Baghbanic, R.Shafiee zadehc, M.Khan soltanic, E.Faraj zadehc, F.khosravic
, N.Hajizadehc
a
b
c
Schiff’s bases (azomethines, imines) belong to a widely used group of organic intermediates
important for a production of chemical specialties. A basic reaction for the synthesis of Schiff bases
involves an aromatic amine and aldehyde. Similarly, reactions of amines with ketones provide
Schiff’s bases of a ketimine type. Pyridine ligands, which have been used in the coordination
chemistry of a variety of metals, occupy a unique position in the synthesis of biologically active
compounds. Here we report the synthesis and characterization of tridentate Schiff-base ligand from
the reaction of 3-hydroxy-2-naphthohydrazied with salicylaldehyde, and pyridine and its complexes
with Co2+ , Fe3+and Cr3+ cations. The complexes were characterized with IR, Uv/Vis and
conductance measurements. Comparison of spectroscopic results for the ligand and complexes and
also visible absorption spectra for complexes suggest that ligand act as a tridentate and coordinates
via two oxygen and imin nitrogen atoms. Comparison of IR and electronic spectra of pyridine and
complexes shows that nitrogen of pyridine coordinates to the metal as well.
Keywords: Schiff-base, Pyridine, Transition metal cations
P-514
Preparation of some complex natural products by use of nickel sulfate heptahydrate as
an efficient catalyst
Shaghayegh Nikoseresht, Bahador Karami*, Saeed Khodabakhshi and Roghayeh Reajabi
Islamic azad university of gachsaran branch, gachsaran, Iran
Catalytic technologies play a vital role in the economic development of the chemicals industry and
transition metal-catalyzed reactions are among the most powerful tools in chemical transformations.
In this work paper, use of nickel sulfate heptahydrate (NiSO4.7H2O) as an efficient catalyst for the
synthesis of benzo-2-pyron derivatives was reported. Benzo-2-pyrons are an important class of
benzo hyterocyclic compounds that are found in structural subunits of more complex natural
products. Also, these compounds were broadly used in the fields of industry and medicine. In this
work paper, a new method for readily preparation of benzo-2-pyron derivatives via the
condensation between phenol derivatives and
-ketoesters using catalytic amounts of nickel
sulfate heptahydrate (NiSO4.7H2O) under solvent-free conditions was reported. The practical and
simple method led to excellent yields of the products under solvent-free conditions and within short
time reaction.
Keywords: Nickel sulfate heptahydrate, Catalyst, Benzo-2-pyrons, Natural products.
290
IICC12
P-515
Microwave-induced combustion synthesis and electrical properties of Yb2O3-doped CeO2
nanopowders
R. Nikpeya,*, M. kashanib and A. Maghsoudipourc
c
Department of Ceramics, Materials and Energy Research Center, Karaj, Iran
a,*
b
Nanopowders have many excellent properties suited for various applications of ceramics such as
gas sensors, rechargeable batteries, fuel cells, and so on. In addition, they can significantly
enhance sintering rates, decrease sintering temperature, and improve optical, electric, and
magnetic properties compared to micrometer size powders. In this research, we have attempted a
new method, the microwave-induced combustion synthesis process, to produce Yb2O3-doped CeO2
nanopowders using cerium nitrate hexahydrate(Ce(NO3)3.6H2O), Ytterbia(Yb2O3), and
urea(CO(NH2)2). The process took only a few minutes (10 min) to yield Yb2O3-doped CeO2 powders.
The nanopowders were investigated by differential thermal analyzer/thermogravimeter (TG/DTA),
X-ray diffractometer (XRD), and AC impedance spectroscopy (IS). The as-received Yb2O3-doped
CeO2 powders revealed that the average particle size ranged from 19 to 34nm, Densification was
performed at 1400 C, in an oxygen atmosphere for 3h. Densification degree and Ionic
conductivity was also found to rise with increasing number of dopants. It was found that the
conductivity gave the highest value when oxygen vacancies were randomly distributed in the lattice.
Keywords: Microwave-induced combustion; Ionic conductivity; Nanopowders; CeO2.
P-516
Hydrothermal synthesis of Praseodymium (III) Coordination polymer with 1,4Benzenedicarboxylic acid and 1,10-phenanthroline
a
S. Niroomanda, M. Khorasani-Motlagha,*, M. Noroozifara, M. Yosefi
The lanthanide complexes have various potential applications in luminescent materials, magnetic
materials, catalysts, and porous material. The use of lanthanide ion as nodes for the construction of
coordination polymers is more significant due to their large radii, high coordination number, and
special luminescent behavior of lanthanide. To date, a great many works have been focused on
using multicarboxylates to form coordination networks. 1, 4-H2BDC (1, 4-benzenedicarboxylic acid)
possesses two carboxylic groups that can be completely or partially deprotonated resulting in
various coordination modes and allowing different dimensional structures. In this paper we reported
hydrothermal synthesis of polymeric complex, [Pr(1,4-BDC)(phen)(H2O)]n (phen=1,10phenanthroline). This complex was characterized by IR, UV-VIS, 1H NMR spectroscopy as well as
elemental analysis. High melting point of this complex proved its high stability due to polymeric
structure.
Keywords: Praseodymium complexes, 1, 4-benzenedicarboxylic acid, 1, 10-phenanthroline,
Lanthanide
IICC12
291
P-517
Synthesis and Characterization of Lanthanum(III) complexes with N-donor ligands
a
S. Niroomanda , M. Khorasani-Motlagha,*, M. Noroozifara
The hydrated rare-earth trichlorides have served as one of the first crystalline hosts for studies of
the spectroscopic properties of the trivalent lanthanide ions. The search for strongly luminescent
lanthanide complexes, which can be exited in the near UV spectral region, motivated the synthesis
of lanthanide (III) complexes containing aromatic N-donor ligands. They are therefore increasingly
used as highly efficient electroluminescent components for light-emitting diodes, luminescence
probes for analytes, labels for proteins and amino acids, and for molecular recognition and chirality
sensing of biological substrates. Lanthanum(III) complex as formulae [La(phen)2Cl3(H2O)2] (1)
(phen=1,10-phenanthroline) were synthesized and characterized by 1H-NMR, UV-VIS and IR
spectroscopy. Treatment of aqueous solution of (1) with Thallium phenylcyanamide salts yields
[La(phen)2L3(H2O)2] (L= pcyd (2), 2-Clpcyd (3), 2,5-Cl2pcyd (4), 2,4-Cl2pcyd (5)).These new
complexes also have been characterized by spectroscopic methods such as 1H-NMR, UV-VIS and IR.
Keywords Lanthanum(III) complex, Cyanamides, 1,10-phenanthroline
P-518
Synthesis and characterization of [Bu4N][MS4ZnBmp] heterobimetallic zinc complex
[M=W/Mo and Bmp=bis(mercaptopyridine)]
Valiollah Nobakht and Azizolla Beheshti *
The tetrathiometalate anions [MS4]2- (M = Mo, W) are known to react many transition metals such
as Cu+, Ag+, Au+, Fe2+/3+, to form a great number of heterobimetallic sulfide clusters. These clusters
are of great interest because of their rich structural chemistry, their relevance to biologically related
systems, industrial catalysis processes, and advanced materials. However, reactions of these anions
with Zinc(II) ion is less explored. In this work we have prepared two heterobimetallic zinc
complexes from the equimolar reaction of zinc(OAc)2.2H2O, [NH4]2[MS4] (M = W , Mo),
bis(mercaptopyridine) [Bmp]- sulfur donor chelating ligand and Bu4N+ as a counter ion, in H2O as a
solvent. These complexes were confirmed and characterized by infra-red, 1H NMR, UV-Vis
spectroscopy and elemental analysis (for tungsten complex). The molecular structure of the
tungsten complex is under progress.
Keywords: Heterothiometallic complex, zinc complex, sulfur donor chelate ligand.
292
IICC12
P-519
Synthesis and characterization of Cu(II) complex with a new hexadentate hydrazone
Schiff base ligand
Hashem Noei and Hassan Hosseini Monfared *
Department of Chemistry, Znajan University 45195-313, Zanjan, I.R.Iran
The chemistry of copper complexes is of interest owing to their importance in biological and
industrial processes. Biological activities may be related to the redox properties of complexes. For
some copper(II) compounds a lower reduction potential seems to be related to an increased
antifungal activity. Copper and dicopper complexes can exhibit the abilities of superoxide
dismutase, catechol oxidase and chemical nucleases. Complexes of copper(II) with Schiff base
ligands are frequently studied, e.g. for their antibacterial properties. Hydrazones, RR'C=N–NR''R''',
are used as intermediates in synthesis, as functional groups in metal carbonyls in organic
compounds and particular in hydrazone Schiff base ligands, e.g. employed in dinuclear catalysts.
Furthermore, hydrazones exhibit physiological activities in the treatment of several diseases such as
tuberculosis. In this study we have synthesized a new hexadentate dentate hydrazone-Schiff base
ligand and its Cu(II) complex. The ligand was prepared from the condensation of isophethalic acid
hydrazide and aldehyde. The Synthesized compounds was characterized by elemental analyses, IR,
1
H NMR and 13C NMR spectroscopic methods.
Keywords: Hydrazone Schiff base, Chelate, Cu(II) complex.
P-520
The synthesis,characterization and studies of ionic complex [Fe(bpy)3]4[Mn(SCN)6]3
N. Noori, A. R. Rezvani*
*Correspoinding Author :Email:[email protected]
Cationic-anionic compounds have played an important role in many catalytic processes. Much of the
works in this area influences the catalytic activity. In this study, the synthesis of the novel complex
[Fe(bpy)3]4[Mn(SCN)6]3, (where bpy=2,2' bipyridine and SCN= thiocyanate) is reported. The
complex was fully characterized by elemental analysis and spectral data including FT-IR, UV-vis,
atomic absorption, conductivity measurement and cyclic voltammetry. The SCN group may
coordinate to a metal through the nitrogen or the sulfur or both (M-NCS-M'). In general, first
transition series, such as Cr, Mn, Fe, Co, Ni, Cu, and Zn form M-N. The CN stretching frequencies
are generally lower in N-bonded complexes (near and below 2050 cm-1) than in S-bonded
complexes (near 2100 cm-1) bonds. The infrared spectrum of this complex shows strong absorption
at 2040 cm-1 corresponding to the νstr CN. Electronic spectrum of this complex in CH3CN shows an
absorption band at 214 nm, which is assigned to(ПП*) bpy ligand.The absorption band in vis
region is assigned to (dd) transition. The results of elemental analysis also consist with the
expected formulation of the complex. The cyclic voltammogram of this complex at 100 mv/s scan
rate shows two metal-based reduction couples at the positive potential. The quasi-reversible
reduction couple of bpy is seen at negative potential.
Keywords: Cationic-anionic compounds, thiocyanate, 2,2' bipyridine, absorption.
IICC12
293
P-521
Synthesis and characterization of new complex of Gadolinium and study of their
properties
A. Nouri Majda,*, SH. Ghamamib, M. Ahadia and M. Fadaa
Departments of Chemistry, Islamic Azad University,Ardabil Branch, Ardabil, Iran
Department of Chemistry, Imam Khomeyni International University of Qazvin, Iran
a
b
Magnetic Resonance Imaging (MRI) is a widely used diagnostic imaging technique. Although
excellent soft-tissue images can be obtained by MRI, use of the contrast agents greatly enhances
the contrast of the images and thereby increasing its diagnostic value. Consequently the
development of the efficient MRI contrast agents has recently drawn ample attention.
Gadolinium(III) schiff base complex synthesized and has been obtained and investigated by infared
spectroscopy(IR), UV-Vis, methods. Comparison of IR bands in ligand and gadolinium complex
confirmed the formation of the gadolinium complexes and allowed to propose its structure. IR
spectroscopy excluded the presence of water molecule in the metal coordination sphere.
Keywords: Gadolinium complex,Schiff base ligand,MRI contrast agent.
P-522
Synthesis nano iron-cobalt spinel oxides by oxalate precursor decomposition
a
c
F.noorimoghadam
Department of Chemistry, University of Tabriz, Tabriz, Iran
B.Shaabani*
Department of Chemistry, University of Tabriz, Tabriz, Iran
Iron-Cobalt spinel oxide nanoparticles (CoxFe3-xO4) with different Fe/Co ratios prepared from oxalate
precursore (Co3Fe3-x)1/3C2O4 .2H2O by metode thermal decomposition. Among spinel ferrites,CoFe2O4
is especially interesting because of the high cubic magnetocrystalline anisotropy, high coercitivity
,and moderate saturation magnetization . The properties of these ferrites are highly sensitive to the
concentration of divalent metal ions, to substituting other metallic ions for the divalent ions and to
the crystallite size, also Cobalt-Iron spinels used for Olefines oxidation. A concentrated solution of
cobaltous and ferrous nitrates under reflux was reacted with an oxalic acide solution in the PH
about 9~11 to get precipitation of oxalates. After drying,the oxalate powders were calcined
different tempraturs from 650-900ºC for two hours. The morphology of the powders determined by
scaning electron microscopy (SEM) and x-ray diffraction (XRD). The obtained particles size are
below 30 nm and can be controlled by the heat treatment time.
Keywords: Spinel, Cobalt ferrites, Oxalat decomposition, Nano crystallitie, X-ray diffraction.
294
IICC12
P-523
The energy level calculation of bond displacement procedure of Zn-Cl on cyclopenta
diene by the use of initial calculation of quantum mechanic and DFT density of function
with NBO analysis
a
*R. Soleymania , M.Nouraliei b and M.Liyaghati delshadb
Chemistry Department, Faculty of sciences, Islamic Azad University, Touyserkan branch, young
researchers club, Touyserkan, Iran (Email:[email protected])
b
Chemistry Department, Faculty of sciences, Islamic Azad University, Touyserkan branch,
Touyserkan, Iran
Initial quantum mechanic calculation on the theory of the level of B3LYP/6-311+G** in order to
measure the displacement procedure bond in Zn-Cl in cyclopenta dien structure shows that the
amount of activation energy for this procedure is 53.4606155 KCAL/mol and the procedure of this
reaction is completly exothermic also,NBO alalysis iadicats that this procedure,is a result of π
electron displacement, and the creation of a new σ bond between Zn-Cl bond and cyclopenta dien
ring. Also bond order is different in this structure and not equal.
Keywords: Ab initio, cyclopenta-1,3-diene, DFT, NBO analysis,labaling
P-524
Schiff base complex sol–gel method for LaMO3(M:Co and Mn) perovskite preparation
with high-adsorbed oxygen
a
S.G.Saremia. H.Keypourb, M.Noroozic*
Department of Chemistry, Payame noor University (PNU), Songhor, Kermanshah, Iran
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan , Iran
c
Research Institute of Petroleum Industry, Kermanshah Research
Center of Oil and Engineering, Kermanshah, Iran
A novel Schiff base complex sol–gel method has been used to prepare LaMO3 (M:Co and Mn)
producing high ratios of adsorbed (or surface) oxygen. The as-prepared gels, characterized by
Fourier transform infrared spectroscopy (FTIR), showed that both lanthanum and cobalt and
manganese ions were complexed before calcinations. IR spectra revealed that CO32- and NO3−
presented on the sample surfaces during heat treatment.High-resolution transmission electron
microscopic (HRTEM) images of all samples showed resolved lattice fringes with the inter-planar
spacing 0.35–0.39 nm of the (0 1 2) plane in hexagonal perovskite. BET surface areas of LaCoO3
nano-crystals were 11.7–18.6m2/g.Carbonate and nitrate which were resulting from the oxidation of
functional groups in the Schiff base complex, can produce gaseous compounds and leave vacant
sites for oxygen in the gas phase to adsorb. 2-Formylpyridine and ethylenediamine (H2NCH2CH2NH2)
were used to form Schiff base N,N_-bis(2-pyridinelidene)ethylenediamine. Lanthanum nitrate
[La(NO3)3·6H2O (99.0%, BDH)] and cobalt nitrate [Co(NO3)2·6H2O (99%, Univar)] were the
precursors for complexation with the prepared Schiff base.
Keywords: Schiff base; LaCoO3 perovskite; Adsorbed oxygen; Lattice oxygen
IICC12
295
P-525
Synthesis and characterization of the new Mn(II) macroacyclic Schiff-base complexes
containing bathocuproin
H.Keypoura, M.Noroozia*, S.G.Saremib
b
a
Complexes of three Mn(II)-containing macrocyclic Schiff base complexes containing a
phenanthroline ligand (L) of he type [MnLn)]2+ have been prepared via [1+1] cyclocondensation of
2,9-dicarboxaldehyde-4,7-diphenyl-1,10- phenanthroline and a number of linear triamines via a
metal-templated reaction and coordination features have been examined. The ligands, L, are 16, 17
and 18-membered pentaaza macrocycles and all the complexes incorporate a 1,10-phenanthroline
unit as an integral part of their cyclic structure. The complexes have been characterized by a variety
of methods including Fourier-transform infrared spectroscopy and, 1H NMR, 13C NMR and CHN
analysis.The Mn (II) ion is effective as a template for the Schiffbase condensation of 2,9dicarboxaldehyde-1,10-phenanthroline and three triamines ligands resulting in the formation of
pentaaza macrocyclic complexes based on the phenanthroline N5 rings (16, 17 and 18). Two fivemembered chelate rings adjacent to the phenanthroline head unit are common to all the
complexes. It appears that this arrangement causes stability of the ternary complex precursor and
partially condensed intermediates, which facilitate cyclization resulting in the pentagonal
environment for metal ion.
Keywords: Phenanthroline; Macrocyclic complex; Schiff base; manganese (II); NMR studies
P-526
Synthesis and characterization of the new Cd(II) macroacyclic Schiff-base complexes
b
a
Complexes of three Cd(II)-containing macrocyclic Schiff base complexes containing a
phenanthroline ligand (L) of he type [CdLn(Cl)]+ have been prepared via [1+1] cyclocondensation of
metal-templated reaction and coordination features have been examined. The ligands, L, are 16-,
17-, and 18-membered pentaaza macrocycles and all the complexes incorporate a 1,10phenanthroline unit as an integral part of their cyclic structure. The complexes have been
characterized by a variety of methods including Fourier-transform infrared spectroscopy and, 1H
NMR, 13C NMR and CHN analysis.The Cd(II) ion is effective as a template for the Schiffbase
condensation of 2,9-dicarboxaldehyde-1,10-phenanthroline and three triamines ligands resulting in
the formation of pentaaza macrocyclic complexes based on the [X]phenanthroline N5 rings (X ¼
16; 17 and 18). Two five-membered chelate rings adjacent to the phenanthroline head unit are
common to all the complexes. It appears that this arrangement causes stability of the ternary
complex precursor and partially condensed intermediates, which facilitate cyclization resulting in the
pentagonal environment for metal ion.
Keywords: Phenanthroline; Macrocyclic complex; Schiff base; Cadmium (II); NMR studies.
296
IICC12
P-527
Synthesis and characterization of the new Zn(II) macroacyclic Schiff-base complexes
b
a
Complexes of second Zn(II)-containing macrocyclic Schiff base complexes containing a
phenanthroline ligand (L) of he type [ZnLn)]2+ have been prepared via [1+1] cyclocondensation of
metal-templated reaction and coordination features have been examined. The ligands, L, are 17-,
and 18-membered pentaaza macrocycles and all the complexes incorporate a 1,10-phenanthroline
unit as an integral part of their cyclic structure. The complexes have been characterized by a variety
of methods including Fourier-transform infrared spectroscopy and, 1H NMR, 13C NMR and CHN
analysis.The Zn(II) ion is effective as a template for the Schiffbase condensation of 2,9dicarboxaldehyde-1,10-phenanthroline and second triamines ligands resulting in the formation of
pentaaza macrocyclic complexes based on the phenanthroline N5 rings (X ¼ 17 and 18). Two fivemembered chelate rings adjacent to the phenanthroline head unit are common to all the
complexes. It appears that this arrangement causes stability of the ternary complex precursor and
partially condensed intermediates, which facilitate cyclization resulting in the pentagonal
environment for metal ion.
Keywords: Phenanthroline; Macrocyclic complex; Schiff base; Zn(II); NMR studies.
P-528
Free Energies of Electron Transfer, Electron Transfer Kinetic Theoretical, Quantitative
Structural Relationships and Electrochemical Properties Studies of Metal Nitride Cluster
Fullerenes M3N@C80 in [X-UT-V][M3N@C80(Pc)n](Pc=Phthalocyanine; n=0,1; M=Y & Sc)
Complexes
Sedigheh Noruzian* and Avat (Arman) Taherpour*
Chemistry Department, Faculty of Science, Islamic Azad University Arak Branch, Arak, Iran
E-mail: [email protected], [email protected]
Organometal derivatization of fullerene species is essential to construct novel organometallofullerene materials for a variety of applications. The supramolecular complexes [X-UT-V] 1-9
and [M3N@C80 (M=Y, Sc) are shown to possess a previously unreported host-guest interaction for
electron transfer processes. To establish a good relationship between the structures of 1-9 with
derivatives of nitride metal cluster as [M3N@C80] (M=Y, Sc) 10-15, an index is utilized, µcs. In this
study, the relationships between this index and oxidation potential (oxE1) of 1-9, as well as the first
and second free energies of electron transfer (∆Get(n), for n=1, 2, which is given by the Rehm-Weller
equation) between 1-9 and the nitride metal cluster with their ferrocene and phthalocyanine
[M3N@C80-(Pc)n]( Pc=Phthalocyanine;n=0,1; M=Y & Sc) 10-15 derivatives as [X-UT-V][M3N@C80R](R: Fc=Ferrocene & Pc=Phthalocyanine; M=Y & Sc) 16-21 supramolecular complexes are
presented and investigated. The first and second free energies of electron transfer and kinetic rate
constants of the electron transfers, ∆G#et(n) and ket (n=1,2), respectively, were also calculated in this
study for [X-UT-V][M3N@C80-R].
Keywords: Fullerenes; Organo-metallofullerenes; Nitride metal cluster derivatives.
IICC12
297
P-529
Catalytic oxidation of sulphide by Iron(III) compounds and H2O2
A. Sezavar and N. Safari *
Heme and nonheme enzymes are common and versatile enzymes in nature that have a range of
biochemical functions including oxygen transport. Common reactions catalyzed by heme and
nonheme enzymes, therefore, include aliphatic and aromatic hydroxylation, epoxidation,
sulfoxidation. Chemical building blocks containing sulfoxide functional groups are particularly useful
for the construction of various important compounds in both bulk and fine chemicals. The extensive
chemistry of sulfoxides and sulfones makes them very useful reagents in organic synthesis in
general and useful synthetic intermediates for the construction of various chemically and biologically
significant molecules in particular. Here we introduced new route for the oxidation of a variety of
aromatic and aliphatic sulfides to the corresponding sulfoxides and sulfones derivatives using H2O2,
TBAO, UHB, as oxidants. We compared these reaction yields in the presence of some Fe and Mo
complexes such as [Fe(DMSO)3(NCS)3, Fe(PPY)3(NCS)3, Mo2(3,5_Di_tertbutyl-Sal-benzamin)2], and
some different metalloporphyrins catalysts. Using these systems as catalyst for the oxidation of
sulfide substrates at room temperature give sulfoxide as major product with yields up to 90%. We
found that the efficiency of the catalyst is strongly influenced by the nature of solvent. We chose
three different solvents; methanol as protic and polar solvent, acetonitrile as aprotic and polar
solvent, and ether as nonpolar solvent, to compare the results. The best result was achieved by the
reaction of dipropyl sulfide with Fe(DMSO)3(NCS)3 in the presence of acetonitrile.
Keywords: Sulfide, Sulfoxide, Catalyst, Metalloporphyrin
P-530
Reactivity and mechanism of bromide oxidation by vanadium bromoperoxidase
functional model complexes: A DFT study
M. Chahkandi a,H. Eshtiagh-Hosseini a*,M. R. Housaindokht a, A. Morsali b
Department of Chemistry, Faculty of Science, Islamic Azad University, Mashhad Branch
E-mail: [email protected]; [email protected]
a
b
The vanadium bromoperoxidase enzyme (VBPO) is a catalyst for the two electron oxidation of
halides, so VBPO has the ability to selectively bromated particular substrates at specific locations on
the phenyl ring. A computational study using the B3LYP method was carried out for the mechanism
of bromide oxidation by a series of oxoperoxovanadium(V) complexes with tripodal amine ligands
(ligands: (1) H3heida=N-(2-hydroxyethyl)iminodiacetic acid, (2) H2ada=N-(2-amidomethyl)
iminodiacetic acid, (3) H3nta=nitrilotriacetic acid, (4) H2pda=N-pyridyl methyliminodiacetate, (5)
Hbpg=N,N-bis(2-pyridylmethyl)-glycine). The key step of reaction is the direct nucleophilic attack of
bromide on a protonated peroxide unit (rate determining step of the catalytic cycle), i.e., the
protonated peroxo is an active site. We discuss the possible mechanisms for transition states, with
particular focus paid on the activation energy barriers. Hydrogen bond formation ability of peroxo
group and basic property of tripodal amine ligands (1-5) are two important factors that affect on
the reactivity of peroxo active site. According to the quantum calculations, catalytic activity of the
studied functional model compounds (1-5) shows the regularity 1>2>3>4>5, that had been
expected from experimental results.
Keywords: Vanadium Bromoperoxidase; Oxoperoxovanadium Complex; DFT; Tripodal Amine
Ligands; Transition State; Activation Energy Barrier.
298
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P-531
Synthesis and Characterization of Metal Oxides Nano Structures (M= Cd and Hg) by
Two Cd(II) and Hg(II) Complexes Containing 2,9-dimethyl-1,10-Phenantroline as
precursors
R. Nozari a, M Ranjbar b*, E. Malakooti a, S. Sheshmani a
Department of Chemistry, Islamic Azad University, Shahr-e Ray Branch, Tehran, Iran
b
Department of Chemical Industry, Iranian Research Organization for Science and Technology,
Tehran, Iran ma_randjbar@ yahoo.com
a
Manufacturing of metals and metal oxides in the form of nanoparticles is one of the most promising
lines of the research in advanced chemistry. In the present investigation reports the novel synthesis
of CdO and HgO nano structures using thermal decomposition of metal complexes, [M(NC)X2], M=
Cd and Hg, NC=2,9-dimethyl-1,10-phenantrolin, X=I and Br, as precursors. The nano structures
were characterized by elemental analysis, FTIR and UV-visible spectroscopy, X-ray powder
diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and
energy– dispersive X-ray (EDX) techniques. The complexes, [M(NC)X2], have been prepared by the
reaction between metal acetate, M= Cd and Hg, and KX, X=I and Br, with NC by both hydrothermal
and sonochemical methods. The results showed that the reaction condition plays important roles in
the morphology and particle size of the complexes. Characterization of the complexes was carried
out by elemental analysis, FTIR, UV-visible and 1HNMR spectroscopy, as well as thermal analysis
(TG/DTA).
Keywords: 2,9-dimethyl-1,10-phenantrolin, Nano structures, Mercury complex, Cadmium complex
P-532
Synthesis and Characterization of Metal Sulfide and Oxide (M=Cd, Hg) Nano-structures
Using Ultrasonic Method
S. Sheshmani a,*, M. Ranjbar b, R. Nozari a, E. Malakoti a
Department of Chemistry, Islamic Azad University, Shahr-e Rey Branch, Tehran, Iran
Department of Chemical Industry, Iranian Research Organization for Science and Technology
Tehran, Iran
a
b
In this study, sonochemical characterizations of nano-particles metal sulfide and oxide (M=Cd, Zn)
from the reaction between thioacetamide ligand, and M(CH3COO)2 (M=Cd, Hg) with potassium
iodide and polyvinyl alcohol were determined. The above-mentioned reactions were done under
room temperature and ambient pressure in an ultrasonic vessel. The nano-structures were
characterized using various dedicated facilities/techniques such as elemental analysis, FT-IR
spectroscopy, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), thermal
gravimetric analysis (TGA), ultraviolet-visible (UV-Vis) spectrum, nuclear magnetic resonance (NMR)
spectroscopy and energy-dispersive X-ray (EDX). Based on the results, potassium iodide and
polyvinyl alcohol were acted as a bridging ligand and substrate, respectively. In addition, the nanopowder of these compounds was prepared from nano-structures by hydrothermal reaction and
calcinations. The results confirmed the formation of nano-structures of metal sulfide and oxide
(M=Cd, Hg) at high yield in absence of high temperature/pressure. It was also found that applied
ultrasonic wave showed the particle size.
Keywords: Sonochemical, Nano-structures, Cadmium, Mercury, Polyvinyl alcohol
IICC12
299
P-533
Synthesis, spectral and theoretical studies of some new zinc and cadmium complexes of
a bidentate ligand
K. Nozarian1 and M. Montazerozohori1, H. Tavakol2 and S. Khani1
2
Department of Chemistry, Faculty of Science, University of Zabol, Zabol, Iran.
1
The field of Schiff base complexes was fast developing on account of the wide variety of possible
structures for the ligands depending upon the carbonyl compounds and primary amines. Many tries
were performed to synthesize symmetric or asymmetric ligands in order to obtain rare coordination
number with mercury and cadmium ions whose importance was mainly due to their ability to form
metal coordination compounds. Recently group XII metal complexes, which contain a stable d10
electronic configuration, have received a lot of attention in the fields of inorganic chemistry,
biochemistry and environmental chemistry. In this work we wish to report the synthesis of some
new four coordinated complexes of zinc halides with the ligand of N,N′-bis((E)-4flourobenzylidene)ethylenediamine. The ligand and complexes were full characterized by physical
and spectral data including microanalysis, FT-IR, UV-Vis, 1H and 13C NMR and conductivity
considerable changes in the UV-Vis, IR and NMR spectra confirm the coordination of ligand. Finally,
optimized structures, molecular parameters and vibrational frequencies were calculated at the
B3LYP/LANL2DZ level of theory.
Keywords: Complex, symmetric, bidentate, p-flourobezaldehyde.
P-534
Catalytic Behavior of Nano Preyssler as an Inorganic Catalyst in Synthesis of Aliphatic
and Aromatic Carboxylic Acids
a
F. F. Bamoharrama,*, M. M. Heravib , M. Roshania and R. Omidiniaa
Department of Chemistry, Islamic Azad University – Mashhad Branch, Mashhad, Iran
b
Department of Chemistry, Alzahra University, Tehran, Iran
Encouraged by our success in work with Preyssler heteropolyacid, it is great interest to know what
occur if the Preyssler anion is used as nanocatalyst. Thus we have synthesized and characterized
silica-supported Preyssler nanoparticles and studied its catalytic activity for a wide range of
reactions. In this work, due to the importance of derivatives of benzoic acid in medicine and
industry, we wish to report the applicability of this catalyst for efficient oxidation of aliphatic and
aromatic aldehydes to the corresponding carboxylic acids under reflux and microwave irradiation.
We compared the efficiencies of bulk and nano form. Our findings showed that the nano Preyssler
catalyst is an effective catalyst surpassing the bulk form and product yields are highest with
electron-withdrawing substituents. The effects of various parameters including catalyst type, nature
of the substitutents, and temperature, were studied and optimum conditions were obtained. In
conclusion, we have reported, for the first time, a new catalytic method for oxidation of aromatic
and aliphatic aldehydes with electron-withdrawing and electron-donating groups to the
corresponding carboxylic acids using an eco-friendly heterogeneous inorganic nanocatalyst. The
advantages of this method are reusability of catalyst, easy work-up and high yields.
Keywords: Nano Preyssler, Catalyst, Heteropolyacid, Carboxylic acid
300
IICC12
P-535
Electrochemical synthesis of new functionalized porphyrin
Samira Osati, Nasser Safari*, Saied Saeed Hosseiny Davarani*
Department of Chemistry, Shahid Beheshti University.G.C, Evin, 1983963113 Tehran, Iran
The functionalization of porphyrin can be achieved with various methodes considering advantages
and disadvantages. Electrosynthesis makes possibility to produce green, selective functionalization
of porphyrins which cannot be simply obtained by conventional synthesis. Catechol units can be
oxidized electrochemically to very reactive forms of o-quinones that can be attacked by nucleophiles
. By anodic oxidation of porphyrincatecholes in the presence of different nucleophiles, such as βdiketones as carbon-centered nucleophiles, modified water soluble porphyrincatecholes would be
synthesized. Using of 2-aminophenol as a bidentate nucleophile leads to formation of six member
hetrocycles of phenoxazine. The present work developed a facile method for functionalizing
porphyrins and the synthesis of new phenoxazine-porphyrin catechol derivatives in good yields and
purity.
Key words: Porphyrins, Catechol, Phenoxazine, Electro synthesis.
P-536
Synthesis and characterization of ZnCdS nanoparticles in mesoporous MCM-41
nanoparticles
A. Pourahmada,*, Sh. Sohrabnezhadb, M. Pakravanc
Department of Chemistry, Islamic Azad University, Rasht Branch, Rasht, Iran
b
c
a
Transition metal sulfides, in particular, exhibit variable and novel optical and electrical properties,
and some of them are used for the fabrication of devices. In 1992, the synthesis of a new family of
nanoporous molecular sieves designated as M41S was reported. MCM-41, one member of this
family, has uniform cylindrical pores in hexagonal arrangement and is produced using rod-like
micelles of cationic surfactant molecules as a template. Due to the regularly hexagonal arrays of
nanoporous channels and changeable pore diameters, MCM-41 has become the particular focus of
extensive investigations, and these properties make MCM-41 material among the best candidates as
the hosts for many guest materials, especially semiconductor nanoparticles. We have studied a
simple method for the synthesis of ZnCdS nanoparticles in MCM-41 nanoparticles. The growth of
nanoparticles was started by ion exchange of MCM-41 in a solution of Zn2+ and Cd2+ ions, followed
by treatment of the exchanged samples with Na2S solution. The samples exhibit blue shifts in the
absorption edges with respect to the bulk samples. In spite of some changes which were
appreciated in the MCM-41 framework, powder XRD results reflect that the zeolite structure is
essentially maintained and the average size of the nanoparticles are 5-6 nm.
Keywords: Semiconductors, Nanocomposites, X-ray diffraction, ZnCdS.
IICC12
301
P-537
Synthesis and Characterization of Vanadyl Tridentate ONO Schiff base complexes
Marziyeh Paliz and Ali Hossein Kianfar*,
Some tridentate vanadyl Schiff base compounds have recently been reported and their structures,
electronic and catalytic properties where investigated. In this work some of tridentate (ONO) Schiff
base ligands and their vanadyl(IV) complexes were investigated. The Schiff base ligands were
synthesized by condensation of 2-aminophenol and salycilaldehyde derivatives in methanol. The
VO(H2O) where (L = tridentate Schiff base ligand) complexes were synthesized via reaction of
vanadyl acetylacetonate and Schiff base ligands in ethanol. The synthesized ligands and complexes
were characterized by IR, UV-Vis and elemental analysis. The vibration of azomethine group of the
free ligands is observed at 1600-1615 cm-1. For the synthesized complexes this band was shifted to
the lower frequencies, indicating that the nitrogen atom of the azomethine group is coordinated to
V(IV). The complexes show an absorption band at about 950-1000cm-1 that related to V=O
vibrational frequency. The vibration of coordinated water is appeared at about 3400cm-1 The
electronic spectra of the Schiff bases and their complexes show an intense band at about 350-400
nm related to azomethine charge transfer transition. Also the complexes show a weak ligand field
transition band in the visible region. The elemental analysis is in good agreement with those
calculated for the proposed formula of synthesized complexes.
Keywords: Vanadyl Complexes, Schiff Base Ligands
P-538
Synthesis and coordination of the Phosphorus ylides to Pd complexes
a
M. Panahimehr, S. J. Sabounchei *
E-mail: [email protected]*
By reaction of the monophosphonium salts of dppm (1,2-bis(diphenylphosphino)methane) and
diphosphonium salts of dppe (1,2-bis(diphenylphosphino)ethane) with the strong base
Na[N(SiMe3)2]
the
corresponding
carbonyl
stabilized
ylides
Ph2PCH2PPh2=L
and
L=PPh2CH2CH2PPh2=L (L= C(H)C(O)C6H4Ph (1),(2) and C(H)C(O)OCH2Ph) (2),(4) were obtained.
Using the stabilized phosphorus ylides Novel palladium(II) complexes were synthesized. The
reaction of these chelates with Pd(COD)Cl2 in dry dichloromethane led to the formation of the
mono
nuclear
Novel
palladium(II)
complexes
[PdCl2(Ph2PCH2PPh2L)]
and
[PdCl2(LPh2PCH2PPh2L)] ( L= C(H)C(O)C6H4Ph (5),(6) and C(H)C(O)OCH2Ph (7),(8)). The FT-IR,
1H, 31P and 13C NMR spectra of all compound have been studied.
Keywords: Phosphorus ylides, palladium(II) complexes, phosphonium salts, dppe, dppm
302
IICC12
P-539
Synthesis of LC-2253 as Ethylene Dimerization Catalyst
a
D.soudbara, M. pirouzi,a A.mechrshavia, M parsab
Research and Development of Arak Petrochemical Company Complex
[email protected]
b
Azad Islamic University of Arak
The butene-1 catalyst converts gaseous ethylene dissolved in a liquid phase into butene-1 which is
the product of reaction. Relevant process is called ethylene dimerization. The only commercial
process is the IFP (Alphabutol process), which is an indication of this largely, used as a comonomer with ethylene for the production of higher strength and higher stress crack resistance
polyethylene resins (LLDPE and HDPE). The ethylene dimerization process uses a homogeneous
catalytic system titanium tetrabutoxide, tetrahydrofurane (as named LC 2253 that purchased
foreigner companys) and triethylaluminum as cocatalyst. In Iran consume 100 tones from this
catalyst in petrochemical companies. The goal of this project is synthesis of this catalyst based on
domestic know-how; therefore titanium tetrabutoxide is the main component of this catalyst was
prepared from reaction of titanium tetrachloride and n-butanol at controlled condition. The best
solvent and amine for synthesis of this catalyst are benzene and ammonia respectively. Control of
moisture in reaction condition for inhibition of gel formation is very critical. The sample was
successfully used for dimerization of ethylene in buchi reactor and pilot plant after addition of
tetrahydrofurane.
Keywords: titanium butoxide; 1-butene; ethylene dimerization; ammonia
P-540
Thermal characterization of various Polyethylene Terephthalate/Clay Nanocomposites
M. Parvinzadeh1, S. Moradian2*, A. Rashidi3, M. E. Yazdanshenas4
Department of Textile, Islamic Azad University, Shahre rey Branch, Tehran, Iran
Department of Polymer and Color Engineering, Amirkabir University of Technology, Tehran, Iran
(Email:*[email protected])
3
Department of Textile, Islamic Azad University, Science and Research Branch, Tehran, Iran
4
Department of Textile, Islamic Azad University, Yazd Branch, Yazd, Iran
1
2
Polyethylene terephthalate (PET) based nanocomposites containing three different types of clays (ie
Cloisite® 15A, Cloisite® 30B and Cloisite® Na+), were prepared by melt compounding. The
influence of type of modified clay on disperseability and thermal properties of the resultant
nanocomposite was investigated by various analytical techniques, namely, X-ray diffraction (XRD),
optical microscopy (OPM), scanning electron microscopy (SEM), differential scanning calorimetry
(DSC), thermal gravimetric analysis (TGA) and dynamical mechanical thermal analysis (DMTA). OPM
images illustrated formation of large sized spherulites in pure PET, while only small-sized crystals
appeared in PET/clay nanocomposites. Decreased glass transition temperatures for all PET/clay
nanocomposites indicate that the amorphous regions of such composites become mobile at lower
temperatures than those in pure PET. Thermogravimetric analyses showed that PET/Na+
nanocomposite was thermally more stable than pure PET, PET/15A and PET/30B nanocomposites
which is indicative of strong intermolecular interactions between PET and Na+ clay.
Keywords: PET; Nanoclay; Hydrophilic; Hydrophobic
IICC12
303
P-541
Incorporation of Hydrophilic or Hydrophobic Nanosilica to Study Disperseability,
Surface and Thermal Properties of Polyethylene Terephthalate/Silica
Nanocomposites
3
4
1
2
Polyethylene terephthalate (PET) based nanocomposites containing hydrophilic (ie Aerosil 200 or
Aerosil TT 600) or hydrophobic (ie Aerosil R 972) nano-silica were prepared by melt compounding.
Influence of type and loads of nano-silica on disperseability, surface and thermal properties of the
resultant nanocomposites was investigated by the use of polarized optical microscopy (POM),
scanning electron microscope (SEM), contact angle measurement (CAM), differential scanning
calorimetry (DSC) and reflectance spectroscopy (RS). Optical microscopy images illustrated that
nano-silica particles tended to increase the size of the spherulites in the PET matrix which is greatly
influenced by type and loads of nano-silica. Contact angle measurement of nanocomposites
demonstrated that surface tension depends on the type and hydrophilicity of nanosilica particles.
Thermal studies of the resultant nanocomposites showed a slight decrease in the melting
temperature compared to pure PET. Optical properties of samples were measured with reflectance
spectrophotometer and discussed.
Keywords: PET; Nano-silica; Hydrophilic; Hydrophobic
P-542
Influence of Clay Type on Surface Properties of Polyethylene Terephthalate/Clay
Nanocomposites
3
4
1
2
Polyethylene terephthalate (PET) based nanocomposites containing various loads (ie 0, 1, 3 and 5
percent by weight) of three differently modified clays (ie Cloisite® 15A, Cloisite® 30B and Cloisite®
Na+) were prepared by melt compounding. The influence of type and content of such clays on
surface properties of the resultant nanocomposite was investigated by various analytical techniques,
namely, atomic force microscopy (AFM), attenuated transform infrared spectroscopy (ATR), contact
angle measurement (CAM) and reflectance spectroscopy (RS). Any possible interaction between
each nanoclay and PET at the surface was elucidated by fourier transform infrared spectroscopy.
AFM studies of the resultant nanocomposites showed increased surface roughness compared to
pure PET. Contact angle measurements on the resultant PET composites demonstrated that the
wettability of such composites depends on hydrophilicity of the nanoclay particles.
Keywords: PET; Nanoclay; Hydrophilic; Hydrophobic
304
IICC12
P-543
Synthesis and characterization of new copper(II) complexes of azo Schiff bases
M. Pasandideh Nadamania, N. O. Mahmoodi *a, K. Tabatabaeiana
a
There is a continuing interest in the chemistry of Schiff bases and their complexes because of their
ability as biologically active substances, liquid crystals, dyes, luminophores and polymer stabilizers.
They readily coordinate with a wide range of transition metal ions, yielding stable and intensely
colored metal complexes, which exhibit interesting physical, chemical, biological and catalytic
properties. Azo compounds are very important molecules and have attracted much attention in both
academic and applied research. For example, azo derivatives and their metal complexes are very
important pigments for synthetic leather and vinyl polymers. Furthermore, Due to the clean
photochemistry of azobenzene, and substantial change in material properties during light
irradiation, it has been investigated as an active component for a variety of applications, such as
lithography, non-linear optical devices and optical switches. According to the above facts, in
continuing to our interest in the synthesis of schiff base compounds we decided to synthesize and
study of the thermal and optical properties of new Photochromic azo Schiff bases and their copper
complexes.
Keywords: Metal complexes; Schiff base; Azo dye; Photochromic azo-azomethine.
P-544
Electronic structure calculation of adsorbate gas molecules on a BN nanolayer
a
M. Pashangpoura,*, M. R. Abolhasanib
Department of Science, Islamic Azad university, Islamshahr Branch, Tehran, Iran
([email protected])
b
Department of Physics, Tarbiat Modares University, Tehran, Iran
A first-principle investigation of the electronic properties of monolayer hexagonal boron nitride (hBN) adsorbing B, N, C atoms and gas molecules of H2O, CO2, NO, NO2, NH3 and H2 is presented. We
have performed first-principles plane wave calculations within density functional theory (DFT) using
pseudopotentials. For full geometric relaxation of the molecules in the vicinity of a BN sheet, we
obtain the adsorption geometry, the equilibrium cohesive energies, charge transfer and density of
states (DOS). We discuss the changes in the density of states as well as the extent of charge
transfer, band gap and finally the exchange energies due to the presence of these adsorptions.
These absorptions affect electronic structure of 2D BN sheet. We can identify which of the
adsorbate molecules is acting as donor or acceptor.
Keyword: BN nanolayer, Density functional theory, Density of state, First-principle study.
IICC12
305
P-545
Environment effect on aggregation behavior of tetra sulfonated copper phthalocyanine
Mahrokh Peer*a, A.Ghanadzadehc, D. Ajlooa, Rezayi-Fardb
a-School of Chemistry, Damghan University, Damghan
b-School of Chemistry, Birjand University, Birjand
c-Departmant of chemistry,factually of science,Guilan university
*[email protected]
Phthalocyanines (Pcs) are interesting and versatile compounds, which found many applications in
industry; first of all as dyes and pigments, and later as photoconducting agents in photocopying
machines.Recently, photochemical behaviour of Pcs in photosensitised oxidation reactions has been
studied. The aggregation is interesting and significant in biology.In this work the effect of ionic
surfactant (cationic and anionic) on the adsorption spectra of copper tetrasulfonatophthalocyanine
and its effect on the decrease of aggregation was investigated as well as addition of salt (0-1M),
concentration and organic solvent effect by using UV-Vis spectrophotometry. The association
constant with surfactants (Ka) is then calculated from the absorption spectra and compared. The
tendency for aggregation of Cu(TSPc)4- in aqueous solutions has been found even at low
concentration 10-5 mol/dm3. The dimerization equilibrium constant K for the process 2[Cu(TSPc)4]/[Cu(TSPc)4-]2 has been found to be 1.04×105. The approximate number of pigment molecule (n)
incorporated into a single micelle was estimated for the micellar surfactants concentration. In
surfactants, HTAB has a more effect on the decay of dimer and in salt effect, KI has a highest
decay of dimer. in organic solvents, solvents with long chain has a more effect on the absorption
spectra and so decrease of dimer. Time effect was in agreement of previous finding that HTAB has
a more effect on the decrease of Dimer/Monomer ratio.
Key words: Copper-tetrasulfonatophthalocyanine, Aggregation, Surfactant effect, Solvent effect
P-546
Synthesis, characterization and Theoretical studies of Trifluoro [(4-hydroxy
benzylidene) aceto hydrazide] Ti (IV) complex
R. Pooseha,*, Sh. Ghammamyb, Kh. Mehrania, F. Salimia and J. Zare Akbaria
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin,
Iran (E-mail: [email protected])
a
b
A new complex of Titanium (IV) of Schiff base ligand was synthesized. The Schiff base reacted with
Ti (IV) of 1:1 (metal:ligand). This complex has been characterized by a number of spectroscopic
techniques such as FT-IR, H-NMR and Thermal behaviors studies (TGA). For more theoretical
studies and comparison of theoretical and experimental data, the structure of this new complex has
been made by GaussView. The saved GaussView files were used as input files for Gaussian, and the
structure of this Titanium complex calculated by Gaussian program with HF method and 6-31G
basis set. The comparisons show good closeness and relationship between theoretical and
experimental data. This points out that the theoretical methods especially Gaussian data can be
used instead of many experimental data.
Keywords: Theoretical studies, Gaussian, HF, 6-31G, Titanium complexes.
306
IICC12
P-547
Nanocasting, template synthesis and structural studies of Cu Salt of Phosphomolybdic
Acid for Aerobic Oxidative of Alcohols
M.R. Poorgholam, R. Fazaeli* and H. Aliyan
The synthesis of porous materials has attracted and still attracts intensive attention, and significant
advances have been made with respect to structural, compositional and morphological control.
Since the discovery of many types of mesoporous silicas, such as SBA-15, KIT-6, FDU-12 and SBA16, porous crystalline transition metal oxides have been synthesized using the mesoporous silicas as
hard templates. We have used 2D hexagonal SBA-15 silicas as hard templates for the
nanofabrication of CuPMo12O40 (CuPMo) salt nanocrystal. Aerobic oxidative of alcohols activated
occurs effectively and selectively with air as the oxidant. CsPMo salt nanocrystal was used as the
catalyst. This reaction provides a new environmentally friendly route to the conversion of alcoholic
functions to carbonyl groups. Aldehydes do not undergo further oxidation to carboxylic acids.
Furthermore, there is no organic waste from the reaction and the isolation procedure is
straightforward requiring only the separation of the organic product from the polyoxometalates and
inorganic salts.
Keywords: Nanocasting,
polyoxometalates (POMs).
Nanoparticles,
Green
chemistry,
aerobic
alcohol
oxidation,
P-548
The spectral investigation of interaction of water – soluble cationic porphyrins with
trinitrotoluene (TNT)
R.Pourfaraj , A. Eslami*
Faculty of Chemistry, university of Mazandaran, Babolsar, Iran
2, 4, 6 - trinitrotoluene (TNT), most common military explosive, is one of the major contaminants of
concerns today mainly because of its persistence in the environment. It is released into the
environment as waste from the munitions and defense industries while it is dangerous as
environmental pollutant because of its well known toxicity. For these reasons, methods of detection
and degradation of traces of TNT is of intense interest. Porphyrins are a large class of naturally
occurring and synthetic macrocyclic compounds with an extensive system of delocalized
electrons. The potential of porphyrin platform to interact with small molecules can be used for the
detection of hazardous, toxic gases, environmental pollutants and nitroaromatic compounds. In the
present study, interaction of a cationic porphyrin, 5, 10, 15, 20-tetra (methyl pyridinum -4-yl)
porphyrin (TMPyP) with TNT have been studied by spectral methods, including absorption and
emission spectra. The analysis of spectral data suggested formation of a 1:1 conjugate between
TMPyP and TNT. The equilibrium constant (binding constant) of this conjugation has been obtained
at various temperatures through evaluation of absorption data. The thermodynamic parameters of
the process, including entropy and enthalpy changes, have been calculated and will be discussed.
Keywords: Cationic porphyrins; Trinitrotoluene; Non-covalent interaction; Binding constants;
thermodynamic parameters.
IICC12
307
P-549
Synthesis and Structural Characterization of Novel 2D Lead(II) Organic-Inorganic
Hybrid
a
H. Pourradi a, B. Shaabani a,*, B. Mirtamizdoust a
Synthesis of Inorganic Compounds Research Laboratory, Department of Inorganic Chemistry,
Faculty of Chemistry, University of Tabriz, Tabriz, Iran
The synthesis and characterization of infinite networks has been an area of rapid growth in recent
years. The motivation behind much of this activity has been provided by the prospect of generating,
by deliberate design, a wide range of purpose-built materials with predetermined structures and
useful properties, for example electronic, magnetic, optical, and catalytic. Herein, a novel 2D
lead(II)
organic-inorganic
hybrid
containing
polydentate
aromatic
amines
[Pb(µ3AcO)(AcO)(ppd)]n(1) (ppd is the abbreviation of para-phenylenediamine) (Fig.1) has been prepared
by the branch tube method and characterized by means of crystal structure determination.
Compound 1 is an infinite polymeric chain in which lead(II) is bridged alternately by the amine and
by acetate anion. Moreover, the coordination number of PbII ions is seven, i.e. PbNO6, with “stereochemically active” electron lone pairs, and the coordination sphere is hemidirected. They also show
that the chains interact with each other through π–π stacking interactions which create a 3D
framework.
Keywords: Lead (II), Organic-Inorganic Hybrids, Hemidirected.
P-550
DFT Calculations and Theoretical Investigations of Cadmium(II) fluorine-substituted
β-diketonate
a
H. Pourradi a, B. Shaabani a,*, B. Mirtamizdoust a
Synthesis of Inorganic Compounds Research Laboratory, Department of Inorganic Chemistry,
Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Theoretical modeling has become an important tool to characterize coordination compounds.
Density functional theory (DFT) method is commonly used to examine the electronic structure of
metal complexes. It meets the requirements of being accurate, easy to use and fast enough to
allow the study of relatively large molecules of metal complexes [1,2]. DFT has shown to be
sufficient for the geometry optimization and calculation of spectral properties. Herein we report a
computational investigation of Cd(II) fluorine-substituted β-diketonate (thenoyltrifluoroacetonate)
and the presence of aromatic amine (dmp) with DFT method. The calculations indicate that
complex has 154 occupied molecular orbitals (MOs). The calculated HOMO–LUMO gap is 0.012 a.u.
Keywords: Theoretical modeling, DFT, Cadmium(II).
308
IICC12
P-551
Synthesis and characterization some new Cadmium(II) Coordination polymers with
nitrogen donor ligands:
a
Mohsen Rafi nezhada, Mohammad Jaafar Soltanian Farda* , Ali Morsalib
Department of Chemistry, Islamic Azad University, Firoozabad branch, Firoozabad, Fars, Iran
b
([email protected])
Some new Cadmium(II) coordination polymers with nitrogen donor ligands such as 3,5 bis(2pyridyl),4-amino,1,2,4-tri azol(2-abpt) and 3,5 bis(4-pyridyl),4-amino,1,2,4-tri azol(4-abpt) has
been synthesized using branched tube and reflux method and characterized by CHN elemental
analysis, IR, 1H NMR,UV-Vis spectroscopy and studied its therma behavior as well as X-ray
crystallography, respectively. The thermal stability of compound was studied by thermal gravimetric
analysis (TGA) and differential thermal analysis(DTA) diagrams too.
Keywords: Cadmium(II) , Nitrogen donor ligand, Coordination polymers
P-552
Host (nanocavity of zeolite-Y)/guest (N2O2-Cu(II), Mn(II) and VO(IV) Schiff base
complexs) nanocomposite materials: Synthesis, characterization and Catalytic
Properties
N. Rafiee and S. Rayati*
Host (nanopores of zeolite)/Guest (transition metal complexes) Nanocomposite Materials (HGNM)
and related materials are one of the subjects of current catalysis research due to their potentiality
as biomimetic heterogeneous catalysts. These encapsulated catalysts are often referred to as
zeozymes as they behave functionally similar to many enzyme catalysts in some selective oxidation.
The finding of efficient catalysts for the selective insertion of one oxygen atom from oxygen donors,
like PhIO, O2, H2O2, t-BuOOH, or NaOCl into various organic molecules, under mild conditions,
remains a difficult challenge in the fields of chemical and biological catalysis. Among the inorganic
mimics of enzymes, metal complexes containing porphyrin, Schiff base, and phthalocyanine ligands
have been investigated as possible alternative catalysts in many oxidation reactions. In the present
investigation, we have isolated Cu(II), Mn(II) and VO(IV) complexes encapsulated in zeolite-Y of a
tetradentate Schiff base ligand (derived from 2,2-dimethylpropanediamine) and characterized by
spectroscopic studies as well as diffraction (XRD) patterns. The catalytic activity of these complexes
in oxidation of hydrocarbons with different oxidant has been investigated.
Keywords: Schiff base, Zeolite, Catalyst, Oxidation.
IICC12
309
P-553
Preparation of Sodium Alginate Nano-particles containing Bovin Serum Albumin
, A. Zare Mirak Abadi b, N. Mohammadpour Duonighi b, S. Sheshmani a, M.
Damavandic
a
Department of chemistry, Islamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
b
Razi Vaccine and Serum Research Institute, Karaj, Iran
Department of chemistry, Islamic Azad University, North Tehran Campus, Tehran, Iran
M. Rahimi Borumand
c
a,*
Alginate, a natural biopolymer extracted from brown algae (kelp) has several advantages which
have made it to be used as a matrix for excavation and delivery of a variety of biological agents.
In present work, we were carry out a systematic study to prepare a new kind of biocompatible and
biodegradable nano-particles for loading Bovin Serum Albumin (BSA), and evaluating their potential
as protein delivery system. In our study a series of alginate nano-particles were prepared. Calcium
chloride (CaCl2) was used as a cross-linking agent, cause of its cationic property, and poly-l-lysine
was also used as polycationic agent to prepare matrix under ionic-gelation process. The influence of
some factors (BSA, polymer, CaCl2 concentration, homogenization rate and pH) in particles size,
morphology, encapsulation efficiency (EE) and loading capacity (LC) were studied. FT-IR was used
to confirm cross-linking processes of polymer with cationic agents and Brad Ford assay was also
used to measure LC and EE. TEM and Z.SIZER were used for morphological and dimensional
studies. It optimum condition the results were as follow; %EE and %LC were 89.25% and 89.23%
consequently.
Keyword: Nano-particles, Sodium alginate, Cross-linking, Poly-l-lysine, Encapsulation
P-554
Synthesis of maghemite nanoparticles from magnetite by mechanochemical method
F. Rahimi, S. A. Kahani*
Department of Inorganic chemistry, Faculty of chemistry,
University of Kashan, Kashan, Iran
Iron oxide exists in a variety of chemical compositions and with different magnetic properties.
Maghemite (γ-Fe2O3) is the most common and intensely researched iron oxide. The maghemite
have physical and magnetic properties and are commonly developed for electronics applications.
Here we propose a new method in preparation of maghemite by mechanochemical reaction. In
mechanochemical method the reaction is carried out at room temperature and also free solvent.
The reaction is carried out by grinding a magnetite in an agate mortar with a pestle at room
temperature. In fact in this method the reactants are magnetite nanoparticles and air and also the
reaction tack placed on the interface of solid and gas phase. Solid phase preparation of maghemite
from magnetite is more desirable because the morphologies of different magnetite nanoparticles
will be controlled the product properties. In this study the products are characterized by X-ray
powder diffraction (XRD), Scanning electron microscopy (SEM) Vibrating sample magnetometery
(VSM). The mean crystallite size was calculated from XRD line broadening using the Scherrer
relationship, the results show of the crystalline size of maghemite nanoparticles is 26-30 nm. The
magnetic hysteresis shows that the magnetization saturation of maghemite is decrease relative to
magnetite. The SEM shows particle size of the synthetic maghemite varied from 40–57 nm.
Keywords: magnetite, maghemite, mechanochemistry, saturation magnetization.
310
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P-555
Synthesis and characterization of palladium (ΙΙ) complexes and their application in
Suzuki coupling
a
N. Rahimia, K. Karamia*
Department of inorganic chemistry, faculty of chemistry, Isfahan university of technology, Isfahan,
Iran
Transition metal catalyzed cross-coupling are fundamental transformation in modern organic
synthesis. Among them, the Pd catalyzed Suzuki reaction is very efficient for the formation of arylaryl bonds, and therefore finds widespread application for the synthesis of molecules possessing
interesting pharmacological or physical properties. In this study, Pd(Oac)2
with tri(otolyl)phosphane are used to prepare a dimmer with acetate bridge, Then the bridge is exchanged
to bromide and chloride. Then the dimer is broken to monomer by P(Ph)3. After removing halides
by Ag(Tfo), the solution is admixed α-keto phosphorus ylide. The solvent is removed and the
complex characterized by IR, UV-VIS and NMR spectroscopy. The synthesized palladium complex
was used in Suzuki coupling to prepare biphenyl derivatives. Our comparison was between donor
and acceptor groups that substituted on arylbromide.
Keywords: Synthesis, Palladium complex, Phosphorus ylide, Suzuki coupling.
P-556
Preparation and characterization of metalloporphyrin nanoparticles using Microwave
Method
Z. Ghasemia R. Rahimib,*, and M. Rabanib
Department of Chemistry, Islamic Azad University of Saveh, Saveh, Iran
a
b
Fabrication techniques of organic molecular nanoparticles have been one of topics in nanoscience
and nanotechnology. Kasai et al. have been established a strategy to control the size of organic
particles in nano level by reprecipitation method. They have succeeded in making organic
nanoparticles such as aromatic compounds, organic dyes and polydiacetylene derivatives.
Alternatively Tamaki et al. proposed a laser processing technique to generate organic nanoparticles
by laser ablation of organic dyes in microcrystal dispersion. It is possible to downsize the porphyrin
crystal to nano level by these techniques and some groups have succeeded in preparing porphyrin
nanoparticles. We report a method for the fabrication of porphyrin nanoparticles. nanoparticles
were produced by a combination of the reprecipitation method and microwave irradiation, termed
the ”microwave method”.The absorption spectra of nanoparticles were investigated. The porphyrin
molecule solutions and nanoparticle dispersions were also used for emission spectroscopy Using a
luminescence spectrometer.
Keywords: Porphyrin, Nanoparticles, Microwave Method
IICC12
311
P-557
Synthesis and Spectroscopic characterization of Some New 3-Chloro-propylene
phosphoric triamides
a
R. Rahimi *a, Kh. Gholivand a, Z. Hosseini a , F. Abdevalia
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115 – 175, Tehran, Iran
(e-mail: rahimi_reihaneh@ yahoo.com)
The widespread researches on phosphoramidates in recent years are due to the different valuable
applications of thes derivatives as prodrug material, insecticides and pesticides, urease inhibitors,
the efficient ligands in coordination chemistry, theoretical chemistry and synthetic purpose. In this
work we synthesized new phosphoric triamides, 3-chloro-propylene phosphoramidic dichloride 1, 3chloro-propylane bis(allylamine) 2, 3-chloro-propylane bis(isopropylamine) 3 and 3-chloro-propylane
bis(tert-butylamine) 4 and characterized by IR, 1H, 13C, 31P NMR spectroscopy and elemental
analysis. Compound 1 was prepared by Kirsanov reaction and compounds 2, 3 and 4 were
synthesized in the reaction of 1 with mentioned amines in 1:4 molar ratio for 4–6 hours. The results
showed that esteric effects caused deshilding of phosphorus nuclei and shilding of amidic hydrogen.
Stretching vibrations of ν(P=O) and ν(C=O) appeared in the range of 1160-1193 cm_1 and 16701694 cm_1 respectively.
Keywords: Phosphoramidate, IR spectroscopy, NMR spectroscopy, Esteric effect.
P-558
Core or/and peripheral protonation of meso-tetrapyridylporphyrins with protic acids: a
comparative UV-vis spectroscopic study
H. Rahiminezhada, S. Zakavib,*, R. Alizadeha
b
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan, Iran
a
In addition to the intrinsically nonplanar porphyrins such as meso-tetra(tert-butyl)porphyrin,
substitution of the core nitrogens, interaction with different σ and π acids, axial ligation and
metallation of the macrocyle have been indicated as causative and influential factors in porphyrin
non-planarity. In the present work, meso-tertrapyridylporphyrins (pyridyl = 2-pyridyl, 3-pyridyl or 4pyridyl) have been prepared and partially or fully protonated with different acids. The shifts of the
Soret and Q(0,0) bands upon the core and/or peripheral protonation of the porphyrins have been
studied in dichloromethane and water. The observed red shifts of the Soret band upon
diprotonation and hexaprotonation of meso-tertrapyridylporphyrins shows the considerable
importance of out-of-plane deformation of porphyrin core on the position of the Soret band in UVvis spectra. Red- or blue shifts of the Q(0,0) bands have been shown to be dependent to a large
extent on the steroelectronic properties of the meso-substituents as well as the electronic effects of
the central acceptors. In conclusion, the results of this study clearly shows that the previous report
on the observation of blue shift of the Q(0,0) band of meso-tertrapyridylporphyrins upon
protonation with strong protic acid in water has been due to the formation of hexaprotonated rather
than a diprotonated species.
Keywords: Meso-tertrapyridylporphyrins, Protonation, Q(0,0), Soret
312
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P-559
Preparation, spectroscopic and electrochemical studies of some new complexes of
zinc(II) and cobalt(II) ions
A. Rahiminia, M. Montazerozohori * and M. Ghaedi
Department of Chemistry, Yasouj University, Yasouj 75918-74831, P. O. Box353, Iran
Schiff base complexes have been amongst the most widely studied coordination compounds in the
past few years. New applications such as antidepressants, antimicrobial, antitumor, antiphlogogistic,
nematocide, and other medicinal agents have been reported based on these compounds.
Furthermore, tetradentate Schiff base complexes are important for designing metal complexes
related to synthetic and natural oxygen carriers. This is due to the fact that Schiff bases offer
opportunities for inducing substrate chirality, tuning the metal centered electronic factor, enhancing
the solubility and stability of either homogeneous or heterogeneous catalysts. In this research we
report preparation of some new complexes of zinc (II) and cobalt (II) ions with the ligand of
bis(trans-cinamaldehydene)-1,2-diaminopropane. The ligand and complexes were characterized by
physical and spectral data including microanalysis, FT-IR, UV-Vis, 1H and 13C NMR, Magnetic
succeptibility and conductivity measurements. FT-IR and NMR spectra of the complexes exhibit
downfield as well as upfield shifts of the free ligand resonances that shows change in geometry
during coordination. The suggested structure of the complexes is pseudo-tetrahedral. Molecular
structures of the complexes have been optimized by molecular mechanic calculations and supported
tetrahedral geometry around the metal ions(II). In final, the electrochemichal behavior of ligand
and complexes in acetonitrile were investigated.
Keywords: Synthesis, Complex, Diaminopropane, cinnamaldehyde.
P-560
Synthesis, spectral identification of some four coordinated complexes of IIB elements
A. Rahmani1, M. Montazerozohori2*, S. Joohari3
2
Department of Chemistry, Yasouj University, Yasouj 75918-74831, P. O. Box353, Ira.
3
Department of Chemistry, Islamic Azad University, Yasouj Branch, Yasouj, Iran.
1
Schiff base compounds constitute an important class of ligands and have been extensively studied
in coordination chemistry mainly due to their facile synthesis and easily tunable steric and electronic
properties. They have occupied a key role in the development of coordination chemistry as seen
from an enormous number of reports on Schiff base complexes, ranging from pure synthesis to
modern physicochemical and biochemically relevant studies of metal complexes. Recent interest in
the design, synthesis and characterization of symmetrical Schiff base complexes with d- block
element derived from the realization that the coordinated ligands around the central metal ions in
natural systems. The aim of the present study is to synthesize and identification of a ligand as
bis(2-nitrophenylmethylidene)-1,2-ethylenediamine and some IIB complexes. These complexes
were synthesized with slowly addition of the ligand to metal salt in ethanol with severe stirring for
3-4h under reflux. The ligand and complexes were characterized by elemental analysis, conductivity
measurements, FT/IR and UV-Vis spectra.
Keywords: Bidentate Schiff base, Zn(II), Cd(II), Hg(II)
IICC12
313
P-561
Immobilization of metalloporphyrins in mesoporous MCM-48 as a heterogenous
catalysts for the oxidation of alkenes
a,b
N.Rahmani khalilia,*, R.Rahimib
Epoxidation of olefins is a widely used process in the chemical industry, because the epoxides are
valuable intermediates for laboratory syntheses as well as chemical manufacturing.
Metalloporphyrins are able to carry out selective oxidation of organics substrates with several
oxidizing agents. Recently, mesoporous materials has attracted much attention as supports due to
their high surface area, well-defined array of uniform mesopores, better dispersion and
regeneration properties. However, due to its narrow pore size distribution and its interwoven and
branched, regular, cubic pore structure, which provides more favorable mass transfer kinetics in
catalytic technologies, MCM-48 seems to be a more interesting candidate for applications than
MCM-41. In this study, synthesis and characterization of Fe and Mn metalloporphyrins encapsulated
into mesoporous MCM-48 investigated. The catalysts were tested in the reaction of cyclohexene
oxidation with hydrogen peroxide. In this regard, the FT-IR, SEM, XRD, UV-Vis spectra and GC were
used for characterization of the above materials. It was found that immobilization significantly
enhances catalytic activity as compared to the homogenous system.
Keywords: MCM-48, Metalloporphyrins, Oxidation catalysts, Cyclohexene
P-562
Synthesis and Structural Characterization of some transition metal(II) complexes
with hydrazide
a
S. Rajaeia,*, Sh. Ghammamya,b , H. Sahebalzamania , Sh. Dexhkoma and F. Siavoshifara
Department of chemistry, Faculty of science, Islamic Azad University, Ardabil Branch, Iran.
b
Department of chemistry, Faculty of science, Imam Khomeini International University
Ghazvine,Iran.
Acid hydrazide exhibit a broad spectrum of biological, bacterial and fungicidal activities.the
complexes of hydrzide on other hydrazine derivatives have great interest due to their analytical,
industrial and pharmacological importance. In this study, the new complexes have been synthesis
by reaction of Hg(II), Pd(II) and Cu(II) with Acetic acid (3-phenyl –allylidene)- hydrazide (L).
Coordination take place through the nitrogen and oxygen groups. All of these ligands and
complexes are characterized by FT-IR, UV-Vis, 1H-NMR spectroscopy and thermal gravitation
analysis (TG, DTA) methods.
Formula of synthesized complexes is [MLn]2+ in than L= hydrazide
ligand , M= Cu, Pd, Hg and n=2.
Keywords: complexes; hydrazide ligand; Synthesis; Characterization; thermal properties.
314
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P-563
ZnO-In2O3 nanocomposite photocatalysts: preparation, characterizations and activity
for 2,4-dichlorophenol photodegradation in water
Nasrin Talebian*, Razieh Ramazan Ghasem
Department of Chemistry, Faculty of Science, Islamic Azad University, Shahreza branch, Iran
Nanocrystalline bicomponent ZnO–In2O3 thin films with various Zn / In ratio have been prepared by
the sol–gel Dip-Coating (SGDC) technique and calcined at 550 oC. Their crystalline structure and
surface morphology of films were determined by appropriate techniques (XRD and SEM
spectroscopies), while their photocatalytic activity (PCA) was tested in the case of the degradation
of 2, 4-dichlorophenol (2,4-DCP) in water. PCA increased with decreasing In2O3. On the basis of
various characterisations of the photocatalysts, the reasons invoked to explain the PCA
enhancement due to In2O3 include a better separation of photogenerated charge carriers, different
crystallite growth processes as a function of Zn/ In ratio and an increased surface acidity inducing a
higher extent of adsorption of the aromatics.
Keywords: Nanocrystalline thin films, sol–gel Dip-Coating, photocatalytic activity.
P-564
Sonochemical preparation and characterization of cadmium(II) coordination polymer
with pyridinecarboxylate and azide ligands
M. Ramezani, A. Morsali*
Department of Chemistry, Payame Noor University, Abhar, Zanjan, Iran
The construction of coordination polymers besed on metal and organic building blocks is a rapidly
developing area of research. Type of ligand, neutral organic e.g. Pyridinecarboxylate and anionic
e.g. azide are used to Synthesize one-two-or three-dimensional polymers. Sonochemistry is the
research area in which molecules undergo a chemical reaction due to the application of powerful
ultrasound radiation (20 kHz to 10 MHz). In the present study we have described synthesize of
cadmium (II) coordination polymer whit 3-pyridinecarboxylate (3-pyc) and azide (NaN ),
[Cd(N )(3-pyc)]n (1) were prepared under thermal gradient condition using the branched tube
method. Characterizations of this compound were done with IR spectroscopy and the thermal
stability of this compound was studied by thermal gravimetric (TG) and differential thermal analyses
(DTA). Structural studies of this compound were done by X-ray crystallography. Nano-structured
compound 1 was synthesized by a sonochemical method. Afther calcination of nano-sizd compound
1 at 500ºC, pure phase nano-sized cadmium(II) oxide has been produced. CdO nano particles in
addition to above method were obtained by thermolyses of compound 1 in oleic acid. The CdO
nano particles were characterized by X-ray diffraction (XRD), SEM, IR spectroscopy.
Keywords: Nano-Structure, Cadmium(II) oxide; Coordination polymer; Crystal structure
IICC12
315
P-565
Synthesis, characterization and solvatochromic properties of new dinuclear complexes
of Cu(II) with bridging azido ligand
Department of chemistry, University of Mazandaran, Babolsar, Iran.
Spectra are a plentiful source of valuable information on the factors influencing the structure and
the reactivity of chemical entities. Spectral investigation of copper(II) chelates of ethylenediamine
and its derivatives have made a significant contribution towards the understanding of factors
determining the stereochemistry, the stability and properties of these important classes of
coordination compounds. Recently we prepared dinuclear copper(II) complexes with “OH” bridging
groups that showed solvatochromism. In this work two dinuclear copper(II) complexes of types [
Cu2(L)2(N3)2](ClO4)2 , (1) and [Cu2(L')2(N3)2](ClO4) (2) where L = N,N'-dimethyl,N'-benzyl-1,2diaminoethane and L'= N,N'-diethyl,N'-benzyl-1,2-diaminoethane have been synthesized and
characterized on the basis of elemental analysis, conductance measurement IR and UV-Vis
spectroscopies The complexes are soluble in the most of solvents and are solvatochromic. Their
solvatochromism properties were studied by UV-Vis spectroscopy. To interpret their
solvatochromism behavior stepwise multiple linear regression (SMLR) method were utilized with
using different solvent parameters models. The results suggested that the donor number (DN)
parameter of solvent has the dominate contribution to the shift of the d-d absorption band of the
complexes.
Keywords: Copper (II) complex, Dinuclear complex, Azido bridged, Solvatochromism.
P-566
Synthesis and solvatochromic studies of mono nuclear copper(II) complexes derived
from diamine and pseudohalides
Department of chemistry, University of Mazandaran, Babolsar, Iran.
Pseudo halide ligands such as N3-, NCO-, NCS- and NO2- can coordinate to the transition metal
atoms in different ways, for example as a terminal ligand or as a bridge and also through different
atom (in case of NCO-, NCS- and NO2-). In this research a series of copper(II) complexes of
[Cu2(X)4(diamine)2] where X= N3−,NCO−,SCN− ,NO2− and diamine stands for N,N'-dimethyl,N'benzyl-1,2-diaminoethane and N,N'-diethyl,N'-benzyl-1,2-diaminoethane have been synthesized and
characterized by elemental analysis, molar conductance, IR and UV-Vis spectroscopies. The
characterization results confirmed formation of dinuclear complexes type shown below in which the
copper ions are penta-coordinated with square pyramidal topology by two N-atoms of the diamine
ligands and three pseudo halide groups. The IR spectra of the complexes showed that pseudo
halide coordinated to the copper center as bridge and terminal as evidenced by two diagnostic
signals in the IR spectra (N3− at 2041 and 2078 cm−1, SCN− at 2096 and 2070 cm−1, OCN− at 2200
and 2170 cm−1 and NO2− at 1346 and 1272 cm-1). The complexes exhibited solvatochromism
behavior as evidenced from UV-Vis spectra taken in different solvents.
Keywords: Copper(II) complex, Diamine, Solvatochromism, Pseudo halide.
316
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P-567
Spectrophotometric study of complexation between four new derivatives of
thioxanthone and some of transition metal ions in Methanol and Acetonitrile
M. Ranjbar a, A Shokrollahi a,*, S. Nasiri b, A. Salimi a
Department of Chemistry, University of yasouj, yasouj 75918-74831, Iran
b
a
Thioxanthone derivatives have been shown to possess useful properties such as the medicinal,
pharmacetical, activators for the photopolymerization and the photoinitiation. As about the
complexation of thioxanthones with metal ions has not been reported in the literature, thus in this
work we studied the complexation of new derivatives of thioxanthones with transition metal ions
such as Cu2+ , Al3+ and Fe3+ in methanol or acetonitrile solutions at 25 ˚C and 0.05 M thrtraethyl
ammonium perchlorate (TEAP) spectrophotometrically. Stoichiometry and overall stability constants
of the obtained complexes have been evaluated by computer refinement of Abs-mole ratio value in
λmax of complex or ligand, using the KINFIT program. The effects of structure of ligands on
complexation were investigated.
Keywords: Spectrophotometric, Complexation, Derivatives of thioxanthone
P-568
Synthesis, Characterization and Kinetic Studies of Uranyl Schiff base complexes
Mohamad Ranjkesh Shoorkaie, Zahra Asadi*
a
Department of chemistry, University of Shiraz, Shiraz, Iran.
(e-mail: [email protected] , [email protected])
Coordination chemistry of Schiff base Ligands has been a fascinating area of current research
interest to the inorganic chemist. Schiff base Ligands from stable complexes with Lanthanides and
actinides. In recent years considerable effort has been developed to preparing well-characterized
complexes of UO22+. Crystal structures of salen and/or salen like transition metal complexes have
revealed that salen and/or salen like derivatives generally act as deprotonated tetradentate ligands
with the N2O2 set of donor atoms capable of effective coordination in a planar fashion. In this work,
four Schiff bases, prepared from salicylaldehyde condensation with 1,2-ethylenediamine, 1,3propylenediamine, 1,2-propylenediamine, 1,2-phenylenediamine and their UO2L complexes were
synthesized by the reaction of Uranyl acetate with Schiff base Ligands. These Ligands and
complexes characterized by 1H NMR, IR, UV–Vis, elemental analysis and TGA. Kinetic of interaction
between phosphines as donor with the uranyl Schiff base complexes as acceptor were studied
spectrophotometrically. An excellent linearity of kobs vs. the molar concentration of the donor, the
high span of k2 values and the large negative values of ∆S≠ suggest an associative (A) mechanism
for the acceptor-donor interaction.
Keyword: Kinetic, Mechanism, Synthesis, Uranyl Schiff base complexes.
IICC12
317
P-569
Synthesis of Useful Contamination-Free Silver Nanoparticle Suspensions by Using
Polyoxometalate
H. Rashidi1,*, A. Ahmadpour1, F. F. Bamoharram2, M. M. Heravi3, A. Ayati1
Department of Chemical Engineering, Ferdowsi University of Mashhad, Mashhad, Iran
2
Department of Chemistry, Islamic Azad University, Mashhad Branch, Mashhad, Iran
3
Department of Chemistry, School of Sciences, Alzahra University, Vanak, Tehran, Iran
1
The objective of this article is to using a Keggin polyoxometalate, H3PW12O40, at different
cocentration, in chemical photoreduction of silver nitrate to synthesize silver nanoparticle
suspension. In this method, Formaldehyde and PVP were used as reductant and stabilizer,
respectively and Keggin acid has the role of promoter. The sizes of prepared silver particles were
around 2–20 nm. According to our results, control of the size of the particles can be achieved via
POM concentration. By increasing the Keggin concentration, the size of synthesized nanoparticles
reduced and the particles made from the more amount of H3PW12O40, had smaller sizes. The
products were mainly characterized for its particle size distribution to provide information on the
optimal conditions of synthesis and sufficient stability against coagulation. Finally, silver
nanoparticles were characterized by transmission electron microscopy (TEM), x-ray diffraction
(XRD) and UV visible. The suspensions of silver nanoparticles prepared by this method are free
from any metal ion contamination, and are suitable for use in semiconductor industry. The
suspensions is suitable to making micro-interconnects in integrated circuits (IC) devices by ink-jet
printing.
Keywords: Silver, Nanoparticle, POM, Keggin, Suspension
P-570
Synthesis٫ purification٫charactrization and biological activity studies of acephate
M. A. Rashno Taei*, S. Ghadimi, M. Jafari
Department of Chemistry, Imam Hossein University,Tehran, Iran.
Acephate is a contact, stomach and systemic insecticide and acaricide, which has intensive effect on
insects. This pesticide reduces the activity of nerve system important enzyme, acetyl cholinesterase,
in insects and livings. Because of this, it is used against differences of sucking and biting insects in
ornamental plants, vegetables and fruits. In this paper, acephate (V), has been synthesized in four
steps, in the first step synthesis of O, O- dimethyl phosphorochloridothioate (II), of starting
materials methanol and thiophosphorylchloride (I), and then ammonization of O, Odimethylphosphorochloridothioate, and then intermolecular rearrangement of O, O- dimethyl
phosphoroaminothioate (III) by methylation agents, and end step is acetylating of O, S- dimethyl
phosphoroaminothioate (IV), by anhydride acid agents. After investigation of the influence of
different factors in the reaction such as temperature, time, solvent and mol ratio of the reactants
and purification of products ,The structure of synthetic compounds have been characterized by 31P,
31
P{H}, 1H, 13C-NMR and IR spectroscopy and GC-Mass. PASS software (1.193 version) has been
used for prediction of biological potency of synthetic compounds. The probability of their insecticidal
activity and acetylcholineesteras inhibition in human and contribution of atoms in reduction or rising
of acetylcholineesteras inhibition were also investigated.
Keywords: Acephate, thiophosphorylchloride, insecticide, inhibition, biological, PASS software
318
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P-571
Transesterification of soybean oil to biodiesel using some modified oxides as a solid
base catalyst
Elnaz Rashtizadeh, Faezeh Farzaneh*
Chemistry Department, University of Alzahra, Vanak, Tehran, Iran
([email protected])
1
Due to the predicted shortness of conventional fuels and environmental concerns, a search for
alternative renewable fuels that are capable of developing an increasing energy demand has gained
recent significant attention. One of these alternative fuels is biodiesel, Monoesters produced by the
transesterification of vegetable oils with short chain alcohol. In order to develop environmentally
benign process and reduce the biodiesel production cost, several classes of heterogeneous catalysts
have been investigated such as immobilized inorganic complexes and enzymes and modified
zeolites. Biodiesel has been the subject of extensive interest as a result of its desirable renewable,
biodegradable and nontoxic properties. In this work, the transesterification of soybean oil with
methanol has been studied using modified oxides such as Al2O3, TiO2 and SiO2. Reaction parameters
such as reaction time, molar ratio of oil to methanol, and amount of catalyst were optimized for the
production of biodiesel. The biodiesel products were analyzed by GC and GC-MS. The conversion for
modified Al2O3, TiO2 and SiO2 were 99.0%, 77.0% and 6%, respectively, with 100% selectivity
toward the biodiesel formation under the optimum reaction conditions.
Keywords: Biodiesel, Transesterification, Solid catalysts, Soybean oil
P-572
Cobalt(III) complex of thioether-containing hexadentatepyridine amide ligand
Mahdieh Rasoulia, Mehdi Amirnasra*, Kurt Mereiterb
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran.
b
Faculty of Chemistry, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna,
Austria (E-mail: [email protected])
a
Nowadays, the synthesis of new flexible N,S-donor ligands capable of adopting various coordination
modes and creating geometric and highly controlled architecture is of great interest [1, 2]. With this
in mind, new Co(III) complexes with the thioether-containing acyclic pyridine amide hexadentate
ligand 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane have been synthesized and
characterized by elemental analyses, IR, UV–Vis, and 1H-NMR spectroscopy. The electrochemical
behavior of this complex, with the goal of solvent effect on the redox properties, is also reported.
The redox potentials of the central cobalt ion show a relatively good correlation with the π-acceptor
ability of different solvents. The influence of the π-acceptor ability of different solvents cause to
redox potentials shift to negative values. This study shows that the spectroscopic and
electrochemical properties of this complex depend significantly on the nature of the solvent (Fig.1).
Interestingly these complexes show a reversible Co(III)-Co(II) redox process (Fig.1). This behavior
is presumably due to the fact that the donating atoms of the hexadentate ligand remain in the
proximity of the central cobalt atom after the reduction of Co(III) to Co(II).
Keywords: Carboxamide, Co(III) Complexes, Electrochemistry, Thioether.
IICC12
319
P-573
Investigation of Catalytic activity of Spinel-type Metal Oxide in reduction of Pnitrophenol (P-NP)
a
b
N. Rasoulia,*, P. Niksokhanb
Spinel structure type oxides have been studied as catalysts for many organic reactions. Various
chemical reactions such as dehydrogenation of hydrocarbons, decomposition of alcohols and
hydrogen peroxides, selective oxidation of styrene involve spinel oxides as catalysts. This work
investigated application of cobalt and iron containing spinel oxide in the conversion of P-NP to P-AP.
The oxide compound was synthesized by citrate gel method and characterized by XRD, FT-IR and
SEM. The conversion process involved room temperature reduction reaction of P-NP by spinel type
oxide as catalyst. The reduction reaction has been monitored by UV-Vis. The reduction rate has
been enhanced in comparison with the reaction carried out in the absence of the catalyst and
complete conversion was achieved in a very short time.
Keywords: Spinel, Catalysis, Reduction, P-Nitrophenol.
P-574
Synthesis and characterization a new lead(II) Coordination polymer with 2,3pyridindicarboxylic acid ligand
a
Fatemeh Rastaghia*, Najmeh Ghanbaria , Mohammad Jaafar Soltanian Farda , Ali Morsalib
Department of Chemistry, Islamic Azad University, Firoozabad branch, Firoozabad,Fars, Iran
b
([email protected])
A new 3D PbII coordination polymer with 2,3-pyridindicarboxylic acid ligand and H2O,
[Pb(L)(H2O)2]n, has been synthesized using a branched tube method and characterized by CHN
elemental analysis, IR, UV-Vis spectroscopy and studied its thermal behavior as well as X-ray
crystallography. The single-crystal X-ray data shows one types of Pb2+ions with coordination
numbers of seven, Pb (1) with holodirected geometries, respectively. The thermal stability of
compound was studied by thermal gravimetric analysis (TGA) and differential thermal analysis
(DTA) too.
Keywords: lead(II) , 2,3-pyridindicarboxylic acid, Holodirected, Coordination polymers
320
IICC12
P-575
Solvent effect on metal-metal coupling in dinuclear complexes
Razmara.Z*
Depatrment of Chemistry,University of Zabol,Zabol,Iran
We synthesized a dinuclear complexe of Co(III) with N2,N 2-propanediyl bis (2,3- butanedione-2imine-3-oxime) and µ-dicyd that is 1,4- dicyanamido benzene and characterization by elemental
analysis, spectroscopies techniqes,IR,UV-vis , 1H-NMR and cyclic voltammetry. For determination
solvent effect on metal-metal coupling study in solvents acetonitril and dimetheyle formmamid
show that with increased electron donor decresead interaction methal-methal coupling. The
voltammogram of the complexe show two subsequent quasireversible reversible reduction couples
corresponding to Co(III/II) and Co(II/I).Both these reduction couples shift to more positive
potentials as the electron- withdrawing ability of the substituent on the phenyl ring increased This is
consistent with the expected decrease in basisity of phenylcyanamide ligand. The ligand field
transition were covered by intence charge transfer bands.
Keyword: dinuclear complexe, solvent effect, positive potentials, reduction couples
P-576
Synthesize,characterization and study of the new cobaloxim complexes
Razmara.Z*
Department of chemistry, university of zabol, zabol, Iran
Abstract:We Synthesize a series of mononuclear complexes of the type trans[Co(py)(DO)(DOH)pnL]PF6 where (DO)(DOH)Pn=N 2,N2-propanediylbis (2,3-butanedione-2-imine-3oxime) and L is 4-bromophenylcyanamide , 2,5-Cl2 phenylcyanamide,4-MeOphenylcyanamide,2,4Me2phenylcyanamide have been synthesized and characterization by elemental analysis,
spectroscopies technigues, IR, UV-vis and 1H-NMR and cyclic voltammetry. The presence of one
sharp and intence absorbtion bond for the cyanamide stretching around 2010 cm-1 -2035 cm -1
provides evidence that phenylcyanamide ligands coordinate end-on (M-NCN-ph).The electronic
absorption spectroa of these complexes show ligand to metal charg transfer(LMCT) band associant
with a Co(III)-cyanamide chromophor. A positive shift in LMCT energy is observed by increasing
electron- withdrawing ability of substituent on the phenyl ring .The ligand field transition (d-d
transition) were coverd by intence charge transfer band. In voltammogram Reduction couples shift
to more positive potentials as the electron – withdrawing ability of the substituent on the phenyl
ring increased This is show decrease in basicity of phenylcyanamide ligand.
Keyword: positive shift, phenylcyanamide, charg transfer, Reduction couples
IICC12
321
P-577
Synthesis, spectral and theoretical studies of some new complexes of Zinc halides
1
M. Razzaghi 1 and M. Montazerozohori 1 , H. Tavakol 2 , A. Hojjati 1
2
Department of Chemistry, Faculty of Science, University of Zabol, Zabol, Iran.
Several Schiff base have been studied in the past because of their wide applicability. The derivatives
of such compounds and their metal complexes, and also after suitable structural modifications, may
be used as bioactive materials for medicines, biological, pharmacological, clinical and analytical
applications. Metal complexes with symmetric compartmental ligands have been the focus of
extensive studies because of their applications in several areas of chemical research. Schiff bases
play a central role as chelating agents for a large number of metal ions, as they form stable
complex with the metal ions. In this work we wish to report the synthesis of some new four
coordinated
complexes
of
zinc
halides
with
the
ligand
of
N,N′-bis((E)-3-(2nitrophenyl)allylidene)ethylenediamine. The ligand and complexes were full characterized by
physical and spectral data including microanalysis, FT-IR, UV-Vis, 1H and 13C NMR and conductivity
notable changes in the UV-Vis, IR and NMR spectra confirm the coordination of ligand. Finally,
optimized structures, molecular parameters and vibrational frequencies were calculated at the
B3LYP/LANL2DZ level of theory. Theoretical data results pseudo –tetrahedral geometry for
complexes.
Keywords: Complex, symmetric ligand, Schiff base, Nitrophenylpropenal.
P-578
Synthesis and solvatochromism of copper(II) complexes with different counter ions
N.Reisi. H. Golchoubian*
Department of Physical-Inorganic chemistry, the university of Mazandaran, Babolsar, Iran
(e-mail : [email protected], [email protected])
The asymmetric tetradentate ligand (L) prepared by the reaction of Acrylamide (CH2=CHCONH2)
and N,N’-dibenzyl-1,2-diamine in methanolic solution and characterized by FT-IR and NMR
spectroscopies. Three complexes of this ligand were synthesized by introduction of an absolute
ethanolic solution of CuX2 (X= ClO4, Br, Cl) into the ligand. The prepared complexes were
characterized on the bases of molar conductance, elemental analysis, FT-IR, NMR and UV-Vis
spectroscopies. The characterization results suggested that in [Cu(L)](ClO4)2 the copper(II) resides
in a square planar environment generated by two nitrogen atoms of the amine group and two
oxygen atoms of the amid moieties. However, in case of X= Br and Cl the structures are octahedron
in which two X atoms are coordinated above and below of the mean molecular plane. The
solvatochromism of these complexes were also investigated in various solvents utilizing UV-Vis
spectroscopy, and results were feeded to SMLR (stepwise multiple linear regression) computer
program to determine the best model to interpret their solvatochromism behavior.
Keywords: Copper(II)
Ethylendiamine
complex;Tetradentate
ligand;Solvatochromism;
MLR;
Acrylamide;
322
IICC12
P-579
Oxidation of hydrocarbons with hydrogen peroxide in the presence of immobilized Mnhydrazone Schiff base complex
a
Adineh Rezaei Bazkiaei a, Hassan Hosseini Monfareda, * and Alireza Aghaeib
Department of Chemistry, Zanjan University 45195-313, Zanjan, Islamic Republic of Iran. Email:
[email protected]
b
Materials and Energy Research Center, 14155-4777, Tehran, Iran.
The activation of C-H bonds of saturated hydrocarbons and aromatic compounds catalyzed by the
metal complexes is an important goal for basic and industrial chemistry. Heterogeneous catalysts
for the oxidations have attracted a lot of attention from researchers because of the advantages
such as easy handling and product separation, catalyst recovery and less level of waste. For these
reasons, the development of new heterogeneous catalysts for oxidation reactions remains a very
active field of research. In this study a new manganese-hydrazone Schiff base complex was
synthesized and immobilized on silica through a covalent bond. This catalyst was evaluated for
oxidation of aliphatic and aromatic hydrocarbons with green oxidant H2O2. Heterogenization of the
complex led to changes in catalyst stability and regioselectivity in comparison with homogeneous
one.
Keywords: Heterogeneous, Manganese complex, Hydrocarbons, H2O2, Silica, Oxidation.
P-580
Synthesis and characterization of a new asymmetrical tripodal amine containing
morpholine moiety and related Cd(II) macrocyclic Schiff-base complex
a
M. Rezaeivalaa,*, H. Keypourb, A. A. Dehghani-Firouzabadic
b
c
The design and synthesis of macrocyclic Schiff-base ligands and their metal complexes are
fascinating areas of research, owing to their importance in basic and applied chemistry. Macrocycles
containing polyamine and pyridine fragments are an important class of compounds due to their
prominent behavior of forming highly stable complexes with a variety of transition metal ions. In
this work, we report synthesis and characterization of a new asymmetrical tripodal polyamine
containing morpholine moiety. The amine was characterized by the FAB-Mass, microanalysis and 1H
and 13C NMR spectroscopy. The crystal structure of new polyamine was determined. Also a new
Cd(II) macrocyclic Schiff-base complex derived from 2,6-bis(2-formylphenoxymethyl)pyridine and
former tripodal amine was obtained. The complex was characterized by elemental analysis, IR and
FAB-Mass spectrometry. The Cd2+ is effective as a template for Schiff-base condensation of 2,6bis(2-formylphenoxymethyl)pyridine and a new tripodal polyamine having a morpholine moiety.
Keywords: Morpholine Moiety, Tripodal Amine, Macrocyclic Schiff-base Complex, Crystal Structure.
IICC12
323
P-581
Synthesis and characterization of a new 22-membered macrocyclic Schiff-base ligand
and a new 21-membered Co(II) macrocyclic Schiff-base complex containing two
piperazine units
a
M. Rezaeivalaa,*, H. Keypourb,*, P. Arzhangib, N. Rahpeymab
b
The preparation and characterization of metal complexes with macrocyclic ligands was the goal of
much research in recent years. In this work, we report synthesis and characterization of a new 22membered macrocyclic Schiff-base ligand derived from N,N'-bis(3-aminopropyl)piperazine and 1,4bis(2-formylphenyl)piperazine in the presence of Mn(II) metal ion (Fig. 1). The analytical data show
that the Mn(II) cation is not retained by the product. Thus it seems that the role of the Mn(II) ion is
to organize the transition state preceding the formation of the L1.The L1 was characterized by the
FAB-Mass and microanalysis. Also in this paper we report the synthesis and characterization of a
new 21-membered macrocyclic Schiff-base ligand derived from N,N'(2-aminoethyl)(3aminopropyl)piperazine and 1,4-bis(2-formylphenyl)piperazine in the presence of Co(II) metal ion.
The complex was characterized by the FAB-Mass, microanalysis and conductivimetry measurement.
Keywords: Piperazine Moiety, Macrocyclic Ligand, Template Synthesis, Schiff-base.
P-582
Synthesis and characterization of new polydentate N, O azo-azomethine ligand and its
Cu(II) complex
Kh. Rezaeian, H. Khanmohammadi*
*
In the last few decades and so on, Schiff base ligands, containing N, O donors, have attracted the
interest of many investigators. Owing to their synthetic and crucial biological importance,
numerous studies have been carried out. Moreover, salicylaldehyde–based azo ligands are the most
considerable class of chelating ligands, with a tremendous number of applications in photorefractive polymer industries, electro-optical devices, heat transfer printing and textile industries. In
addition, their ability to bind toxic and heavy metal ions has been subject of significant interest in
recent years. The present work thus manifests synthesis of new Schiff base ligand,H4L, prepared
by condensation of N, N, N', N'-tetrakis (2-aminoethyl)-2,2-dimethyl propane-1,3-diamine (tdmtn)
with 1-(3-formyl-4-hydroxyphenylazo)-4-Nitrobenzene in ethanol solution. The synthesized azo
ligand was proposed in accordance with the elemental analysis, 1H NMR, IR, UV-Vis spectral data.
Furthermore, a new complex of copper (II) was also obtained by direct reaction of H4L and Cu (II)
ion in ethanol. The resultant complex was identified via IR and UV-Vis spectroscopy and C, H, N
elemental analysis.
Key words: Azo-azomethine; Copper complex; Polydentate ligand; Schiff base
324
IICC12
P-583
Synthesis of Metal Complexes of a New Asymmetric Potentially Heptadentate (N7)
Tripodal Ligand
Amir Ahmad Rezaeia, Sadegh Salehzadeha,* and Reza Golbedaghib
a
b
Faculty of Chemistry, University of payame Noor, Hamedan, Iran
The most thoroughly studied tripodal compounds are the transition metal complexes of potentially
heptadantate Schiff base ligands derived from condensation of tren, tris(2-aminoethylamine), with
various suitable aldehydes. Previously we have reported the synthesis and characterization of a
number of metal complexes of potentially heptadentate(N7) tripodal Schiff base ligands. In this
work we report the synthesis and characterization of a new tripodal heptadentate(N7) ligand and
related complexes with a number of metal ions. Firstly, (2-aminoethyl)bis(3-aminopropyl)amine
(ppe) was condensed with 2-formylpyridine in EtOH as solvent in the room temperature. Then
NaBH4 was added to above solution to reduce the resulting Schiff base. After purification and
evaporation, a solution of appropriate metal ion(Cu2+,Ni2+) in MeOH was added. The synthesized
complexes was characterization by IR, mass, and microanalysis in both cases.
Keywords: Asymmetric, Tripiodal, Heptadentate ligand, Condensation reaction, Reduction
reaction.
P-584
Synthesis and characterization of magnetic nanoparticles α-Fe2O3 by sol-gel method
H. Rezaeia, A. Hosseinianb, A. R. Mahjouba,*
Tehran, Iran
a
b
Hematite (α-Fe2O3) is the most stable iron oxide with n-type semiconducting properties (band gap
Eg = 2.1eV) at ambient conditions. Its potential applications have been explored in fields including
photocatalysis, gas sensors, lithium ion buttery and magnetic materials production. The syntheses
of the nanoparticles of magnetic metal and metal oxides have been reported in recent times by
using different chemical methods, viz. sonochemical, solvothermal, microemulsion, etc. The sol–gel
method is an effective way to prepare nanoparticles of inorganic oxides. These nanoparticles widely
used in catalysts, gas sensors, photoelectrodes for solar energy conversion, medical imaging, drug
targeting and other biological applications, etc. This is a report on the preparation of α-Fe2O3
nanoparticles by sol–gel method. In this work, α-Fe2O3 nano-size powder is synthesized using
Fe(NO3)3.9H2O and oxalic acid [(COOH)2.2H2O] as precursors with ethanol as a solvent. The process
involves gel formation, drying at 100˚C for 24 h to form Iron oxalate dihydrate [Fe2(C2O4)3.2H2O]
and its decomposition at 500˚C for 30 min to yield α-Fe2O3 powder. Other organic acids were used
to prepare α-Fe2O3 nanostructures. These nano powders were characterized by scanning electron
microscopy (SEM), X-ray powder diffraction (XRD) and the Infrared spectroscopy (IR).
Keywords: α-Fe2O3, Nanostructures, Sol-gel method, Oxalic acid, SEM, XRD.
IICC12
325
P-585
Epoxidation of cyclooctene by Ni(II) and Cu(II) macrocyclic Schiff base complexes
immobilized on montmorillonite as a heterogeneous catalyst
Behnam Rezazedeha, Alireza Banaeia, Abolfazl Bezaatpour*b
a: Payame Noor University, Ardabil, 5619914814, Iran
b: Department of Chemistry, Faculty of Basic Science, University of Mohaghegh Ardabili, Iran.
Metallomacrocycles in homogeneous solution or immobilized in solid supports are capable of
carrying out redox catalysis under ambient conditions. Ni(II) and Cu(II) complexes of 14-,15- and
16- membered diaza dioxa Schiff base macrocyclic ligands were synthesized and immobilized on
sodium montmorillonite. The heterogeneous catalysts were characterized by IR, DRS and atomic
absorption spectroscopy (AAS). Investigations of the d-d transition of catalysts show that in all
cases the nickel (II) and copper (II) 14-,15- and 16- membered diaza dioxa Schiff base complex is
mainly physically entrapped within the matrix. All of the heterogeneous catalysts have been tested
in the catalytic epoxidation of cyclooctene with tert-butylhydroperoxide (TBHP) as an oxidant
quantitatively with 100% selectivity toward the corresponding epoxide under mild conditions.
Repeated runs of the catalysts were carried out three times and the obtained results showed that
these catalysts are a robust and stable heterogeneous catalysts and can be recovered quantitatively
by simple filtration and reused without loss of its activity.
Keywords: Ni and Cu (II) Schiff base macrocycle ; epoxidation ; montmorillonite, heterogeneous
catalysts
P-586
Synthesis and characterization and considering spectroscopy (Mo- S- CuI -SCN-CuII) :of
crystal structural new clusters
M. rezazadeha* M. esmhosseinia, and A. azimian Freidani
Department of Chemistry, Urmia University, Urmia, Iran
a
Heterothiometallic clusters with many fascinating configurations can be prepared by liquid or solid
state reaction methods. MS4 2− ions coordinate to the neutral species M- X (M = Cu+, Ag+; X = Cl−,
Br−, I−, CN−, NCS−). We are currently interested in synthesis and reactivity of cluster derivatives
which in that CuI by SCN- coordinates to CuII. [NH4]2MoS4 (1gr) was dissolved in pph4Cl in H2O
(50ml), and the solution subjected to pumping for 2 hr to remove NH3.H2O was added to replace
that lost due to evaporation, and the reaction mixture filtered into i-PrOH (100ml). The precipitated
product was isolated by filtration, washed with i-PrOH and Et2O and dried in vacuum. prepared
(PPh4)2MoS4 reacted with CuCl in acetone (150 ml) to form (PPh4)2MoS4(CuCl)3 (1) then (1) and
KSCN were dissolved in aceton after the reaction mixture had been stirred for 30 min at room
temperature added to CuBr2 had been stirred for 4 hr, the deep violet solution was filtered to
remove the precipitated KCl and the filtrate was evaporated by vacum pump. A combination of
Infrared and Uv/visible and 15P NMR spectroscopy can be used effectively to determine structure of
the Mo-S-CuI-SCN-CuII in which, CuII coordinate to CuI through N- atom of SCN-.
Keywords: Synthesis, Cluster, Crystal structural, Synthesis, thiomolybdate.
326
IICC12
P-587
Synthesis of [TBA]4[PW11FeO39]nH2O/SiO2 composite and its catalytic performance in
oxidation of alcohols with H2O2
M. Riahi, B.Yadollahi*, S.Tangestaninejad
Selective oxidation of alcohols is of great significance to the synthetic organic community. The
development of heterogeneous catalysts for the liquid phase oxidation of organic compounds is a
challenging goal. Transition-metal-substituted polyoxometalates (POM) have attracted much
attention as oxidation catalysts due to their unique physical–chemical properties such as thermal
and hydrolytic stability, motile acidities and red-ox potentials, etc. One of the disadvantages of
POMs utilization as homogeneous catalysts is the difficulty of their separation from reaction mixture
and their inevitable loss during recycling. The attempt to heterogenization of homogeneous catalyst
as alternatives to more traditional reagents and catalysts has been one area of research that has
seen increasing interest. Substantial efforts have been done for the incorporation of POMs into the
suitable inorganic solids have been reported as an effective method to overcome the mention
problems. A polyoxometalates – composite was prepare by sol-gel technique and characterized by
IR, UV, SEM and XRD. The characterization results reveal that the [TBA]4[PW11FeO39]nH2O disperse
in the silica network and its structure remained intact after formation of the composite. This
composite used as an efficient heterogeneous catalyst for oxidation of alcohols by H2O2.
Keywords: polyoxometalate, composite, catalysis, oxidation, alcohols
P-588
Preparation of Perovskite-type LaMO3 (M= Fe, Co, Mn) Nanoparticles Through the
Decomposition of Binuclear La[M(C2O4)3].n H2O Complex under Microwave Heating
Z. Roostai, F. Riazi, Z. Oliasami and S. Farhadi*
In this research, the bimetallic La[M(C2O4)3].n H2O coordination compounds with M= Fe, Co, Mn)
were prepared by mixing of K3[M(C2O4)3] with aqueous solutions of La(NO3)3 and were used as
the precursor for the synthesis of LaMO3 nanoparticles via their decomposition under microwave
heating. Microwave-assisted decomposition of La[M(C2O4)3].n H2O complexes in the presence of
SiC as a strong microwave irradiation resulted in single phase perovskite-type
LaMO3
nanoparticles within 15-25 min. The decomposition products were characterized by XRD, FT-IR
and TEM. The XRD patterns of products showed only the peaks corresponding to perovskite-type
LaMO3. The perovskite synthesized is in an essentially pure phase, as evidenced by its XRD. No
peaks attributable to La2O3 and/or M2O3 and unreacted precursor materials were detectable. FTspectra of the samples were examined to confirm the nature of decomposition products. In the
FT-IR spectrum of products, there are two strong absorptive bands in the range of 400-600 cm-1.
These bands correspond to M–O stretching and O–M–O bending vibrations of MO6 groups in
perovskite LaMO3 respectively. The SEM image reveals that powder is composed of loosely
aggregated extremely fine particles. From this image, it is evident that particles have a narrow
nano-size distribution and homogeneous shape. TEM confirms that LaMO3 particles possess
semi-spherical morphology and a narrow distribution of sizes bellow 100 nm.
Keywords: Perovskite-type Oxides, Microwave heating, Nanoparticles, Heteronuclear complexes
IICC12
327
P-589
Solid-state Decomposition of the Bi[Fe(C2O4)3].nH2O Precursor under Microwave
Irradiation: a Novel Route for Synthesis of Pure BiFeO3 Nanopowder
Z. Roostai, Z. Oliasami, F. Riazi and S. Farhadi*
Among all multiferroics, BiFeO3 that exhibits the coexistence of ferroelectric and antiferromagnetic
orders above room temperature has received great attention due to its relatively high Neel
temperature (TN~375 °C) and Curie temperature (TC~830-850 °C). In recent years various wet
chemical methods have been developed to prepare BiFeO3 nanopowders. However, each of these
methods has its own advantages and limitations. In this work, pure BiFeO3 nanopowders were
synthesized through microwave-induced solid state decomposition of Bi[Fe(C2O4)3].nH2O precursor
in the presence of SiC as a secondary microwave absorber within a very short reaction time of 16
min. The product was characterized by a variety of techniques such as TGA-DTA, XRD, FT-IR, SEM,
TEM, EDX, UV-Vis spectroscopy and magnetic measurement. The magnetic measurement confirms
that the product shows a weak ferromagnetic order at room temperature, which may be ascribed to
the size confinement effect. The DTA and DSC results confirm multiferroic nature of the prepared
BiFeO3 nanopowder with Neel temperature at 370°C and Curie temperature at 830 °C. The BiFeO3
prepared by this method showed a strong absorption band in the visible region. In conclusion, a
simple, fast and energy efficient method has been reported for the preparation of BiFeO3
nanopowder under microwave heating.
Keywords: Nanopowder; BiFeO3; Chemical synthesis; Perovskite-type oxide; Multiferroic
materials; Microwave heating.
P-590
Photocatalytic degradation of methylene blue with CuCr2O4 and CoCr2O4
nanocrystallites
A. Roshan, Sh. Fathi, A. Fallah Shojaee*
Copper chromite (CuCr2O4) and cobalt chromite (CoCr2O4) nanocatalysts were prepared by citric
acid (CA)-assisted sol–gel method. Techniques of X-ray diffraction (XRD), scanning electron
microscopy (SEM), and transmission electron microscopy (TEM) have been employed to
characterize the as-synthesized nanocatalysts. The XRD results indicated that the particle size of
CuCr2O4 is about 28-32nm and the particle size of CoCr2O4 is about 32-38 nm. Degradation of
methylene blue is performed by (CuCr2O4) and CoCr2O4 nanocomposites under ultraviolet radiation.
CuCr2O4/UV-based and CoCr2O4/UV-based photocatalysis was simultaneously able to oxidize the
dye, with an almost complete mineralization of carbon and of nitrogen and sulfur heteroatoms. The
results showed that the rate of degradation of methylene blue with cocr2o4 higher as compared to
that of CuCr2O4. The photocatalytic activity were carried out under varying parameters such as
irradiation time, pH of the solution, catalyst amount, substrate concentration and the H2O2
presence.
Keywords: Nanocrystallites, Photocatalytic degradation, Methylene blue, UV light, CoCr2O4,
CuCr2O4
328
IICC12
P-591
Synthesis, Spectroscopic Characterization and Crystal Structure of a New
phosphorylamidate[(C6H4(2-CH3)NH)2P(O)(O)(O)P(NH(C6H4(2-CH3)))2]
M. Rostami Chaijan*, M. Pourayoubi, H. Eshtiagh-Hosseini
Compounds with phosphorus-containing structures are an important part of chemistry, because of
their applications in medicine, fertilizers, pesticides and plant growth regulators. A new
phosphorylamidate ligand with formula C28H32N4O3P2 [(C6H4(2-CH3)NH)2P(O)(O)(O)P(NH(C6H4(2CH3)))2] has been synthesized and characterized by 1H, 13C and 31P{1H} NMR, IR and single crystal
X-ray diffraction. Single crystal X-ray analysis shows that it belongs to monoclinic system, space
group P21/c, with a = 14.2621(6) Å, b = 15.7029(11) Å, c = 13.8401(8) Å, β = 118.915(4)º, Z = 4.
The phosphorus atoms exhibit a tetrahedral configuration and the nitrogen atoms are practically
planar. The molecule exists as an extended H-bonded chain which is produced by intermolecular
PO…HN hydrogen bonds.
Keywords: Phosphorylamidate, Crystal structure, NMR, PO…HN hydrogen bond
P-592
Syntheses, Spectroscopic Characterization and Crystal Structure of a New OrganotinPhosphoramidate[(4-NO2-C6H4C(O)NH)(OC4H8N)2PO]2Sn(CH3)2Cl2
M. Rostami Chaijan*, M.Pourayoubi, H. Eshtiagh-Hosseini
Organometallic compounds comprise an important class of antitumor agents. The chemical
properties, biological significance, industrial importance and structural characterization of
organotin(IV) complexes are well documented. A new Organotin (IV) complex with formula
C32H48Cl2N8O12P2 Sn [(4-NO2-C6H4C(O)NH)(OC4H8N)2PO]2Sn(CH3)2Cl2 was synthesized and
characterized by IR, 1H, 13C, 31P{1H} NMR spectroscopy and single crystal X-ray diffraction. Single
crystal X-ray analysis shows that it belongs to monoclinic system, space group P21/c, with a =
15.9281(10) Å, b = 8.3865(5) Å, c = 15.9242(10) Å, β = 103.9340(10)º, Z = 2. The Sn
coordination geometry is octahedral. The Sn atom in this compound is located in the inversion
center making half of the molecule related by symmetry. The distances Sn-O, Sn-Cl and Sn-C are
within expected values. The O-Sn-O angle is trans (180°), but the Sn-O-P angles are about 145°.
Keywords: Organotin(IV) complex; NMR spectroscopy; X-ray crystallography, Phosphoramidate
IICC12
329
P-593
Synthesis and crystal structures of new complex pipyrazinum thiodiacetate Cerium (III
) Obtained ligand proton transfer
Shahideh Rostamia ,Mohammad Ghadermazib*
Department of Chemistry , University of Kurdistan ,Sanandaj, Iran
b
Department of Chemistry, University of Kurdistan ,Sanandaj, Iran
a
Crystal engineering is the design of crystal structure for specific purposes and applications. In order
to work in crystal engineering, it is necessary to understand supramolecular chemistry widely.
Supramolecular chemistry is the chemistry of the intermolecular bond. Scroll through a variety of
intermolecular interaction has been proven that hydrogen bonds due to having the characteristics of
power and graft suitable for the main role in this field plays. In this work use the 2,2' thiodiacetic
acid and suitable amine: pipyrazine in order to induce proton transfer and using this combination
for coordination with Cerium. After the synthesis of complex use the spectroscopy methods (NMR,
IR, X-ray diffraction) to identify and determine the composition structure. Cell parameters:
a = 6.4361(7) , b = 11.1135(12) , c = 12.5627(14) ,
α = 96.693(4) °, β= 104.646(3) °, ४ = 101.192(3) °, Z= 1.
Keywords: Crystal engineering, Supramulecular chemistry, Proton transfer compound, X-ray
diffraction.
P-594
Synthesis, Characterization and Crystal Structures of New [Re(CO)3(diimine)Cl]
Complexes
A. Rostami-Vartoonia, V. Mirkhania,*, R. Kiab, S. Tangestaninejada, M. Moghadama, I.
Mohammadpoor-Baltorka
a
b
Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
The photochemistry and photophysics of diimine-Re(I)-tricarbonyl complexes are well established.
These complexes have been used as electroluminescent materials in OLED-type devices. The
synthesis of six tricarbonylrhenium(I) complexes with N,N'-bis(2-bromo, 4-bromo, 4-chloro, 2methoxy, 3-methoxy and 4-methoxybenzaldehyde)-1,2-diiminoethane Schiff base ligands have been
investigated in this study. These complexes have been fully characterized by FTIR, 1H NMR, 13C
NMR and UV-Vis spectroscopy, elemental analysis and X-ray diffraction analysis. The rhenium metal
center has an almost ideal octahedral coordination sphere with a facial arrangement of three
carbonyl groups in the synthesized complexes. The C=N bond distance values in the complexes are
slightly longer than those observed in free Schiff base ligands. Due to the donor character of the
chloride ligand, the length of the axial Re-C bonds is slightly shorter than the values of the
equatorial Re-C bonds. The crystal structures of complexes are stabilized by intermolecular C-H…Cl
and C-H…O hydrogen bonds. The remarkable features of the 2-bromo, 4-bromo and 4-chloro
substituted complexes are short intermolecular halogen-oxygen contacts.
Keywords: Tricarbonylrhenium(I) Complexes, Schiff Base, Diimine Ligands, X-ray Crystallography
330
IICC12
P-595
Proton NMR study of the stoichiometry, stability and thermodynamics of complexation
of Na+ ion with 15-crown-5 in binary acetonitrile–nitrobenzene mixtures
Roshanak rostamiana,*, Mohsen Irandoustb and Saaide amiric
Department of Chemistry, University of Razi, Kermanshah, Iran
b
Department of Chemistry, University of Razi, Kermanshah, Iran
c
Department of Chemistry, University of Payamenor, Ardebil, Iran
a
Proton NMR was used to study the complexation reaction of Na+ with 15-crown-5 (15C5) in a
number of binary acetonitrile (AN)–nitrobenzene (NB) mixtures at different temperatures. In all
cases, the exchange between free and complexed 15-rown-5 was fast on the NMR time scale and
only a single population average 1H signal was observed. The formation constants of the resulting
1:1 (ML) complexes in different solvent mixtures were determined by computer fitting of the
chemical- shift mole ratio data. There is an inverse relationship between the complex stability and
the amount of acetonitrile in the solvent mixtures. The enthalpy and entropy values for the
complexation reaction were evaluated from the temperature dependence of formation constants. In
all solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized.
The T∆S versus ∆H plot of all thermodynamic data obtained shows a fairly good linear correlation
indicating the existence of enthalpy–entropy compensation in the complexation reaction.
Keywords: 15-crown-5, Na+ Ion, Proton NMR, Stoichiometry, Formation Constant, Thermodynamic
P-596
Removal of heavy metals from aqueous solutions using preparation of maleic anhydride
polymer ligands modificated with pyrrole
a,b,C
M.H.Nasirtabrizia*, S. Mohabalizadehb, S. Rostamzadeh mansourc
Departments of Chemistry, Islamic Azad University, Ardabil Branch, Ardabil, Iran,
E-mail: [email protected])(
The chelation of poly(maleic anhydride-co-monomer) have excellent adsorption property for metal
ions are especially applied widely in separation and removing of heavy metal ions. In this work, the
copolymers of maleic anhydride (MAN) with different monomers such as methylacrylate (MA),
ethylacrylate (EA) and buthyl acrylate (BA) were synthesized by free radical polymerization method
in Ethyl acetate solution using azo (bis iso butyro nitrile) (AIBN) as initiator at 70 ±5 0C . Then,
copolymers of maleic anhydride (MAN) have been modified by incorporation of salt of pyrrole
groups through the maleic anhydride (MAN) motieties. The Structure of all the polymers were
characterized by FT-IR, ¹H-NMR , DMTA spectroscopic techniques. With the incorporation of the
pyrrole groups in the polymer side chains, a series of novel modified polymer containing new
properties are obtained, that can find some applications in polymer industry. The results obtained
suggested the treated grafted copolymers possessed good chelating properties toward different
metal ions. This suggested that such polymers could be accepted for practical uses.
Keywords: Maleic anhydride, Pyrrole, Removal heavy metals, 1H- NMR , FT-IR, DMTA
IICC12
331
P-597
Synthesis and characterization of (Mo & W) doped vanadium oxide nanotubes
a
Roya rouhani a,* and Hamid reza Aghabozorgb,*
Faculty of chemistry, Islamic Azad University-North Tehran Branch,Tehran, Iran
b
Inorganic nanotubes have potential application in catalytic processes and electrochemical devices
due to their physicochemical properties. Among them vanadium oxide nanotubes have high
potential application in electrochemical devices and catalytic processes. Doping of molybdenum and
tungsten into these nanotubes could offer the possibility to change the electrochemical properties of
them. In this work, for the first time molybdenum and tungsten were doped into vanadium oxide
nanotubes up to 50% doping level using a sol-gel process. The synthesized nanotubes were
characterized by X-ray diffraction, elemental analysis and scanning electron microscopy. The results
show that the synthesized samples have tubular morphology and multiwall structure.
keywords: vanadium oxide nanotubes, X-ray diffraction, Scanning electron microscopy,
molybdenum and tungsten
P-598
Synthesis and characterization of nickel oxide nanoparticles by complexationprecipitation method
L.sabaghzadeh a ,M.M.kashani motlagh b,*, and A.A.yuzbashi c
b,*
c
Department of Materials & Energy Reaserch Center, Karaj, Iran
a
Nanostructured materials have been extensively explored for the fundamental scientific and
technological interests in accessing new classes of functional materials with unprecedented
properties and applications. In recent years there has been an increasing interest in the synthesis of
nanosized crystalline metal oxides because of their large surface areas, unusual adsorptive
properties, surface defects and fast diffusivities. Nickel oxide is a very important material
extensively used in catalysis, battery cathodes, gas sensors, electrochromic films, and magnetic
materials. Several methods (mechanical or chemical) have been used and developed for
synthesizing crystalline oxide powders in nanoscale dimensions. The present investigation reports,
the synthesis of NiO nanoparticles obtained by complexation-precipitation method using ammonia
as complexing agent. The reactions were carried out at temp 70 °C in solution and finally calcined
at 300 and 400 °C. As a result of heating there was observed a change in size and morphology of
the nanoparticles. The results showed that using this method, NiO nanoparticles with uniform size
distribution and shape can be prepared. The samples were characterized by XRD, IR spectroscopy
and scanning electron microscopy.
Keywords: Nanoparticles, NiO, Complexation- Precipitation, Scanning electron microscopy (SEM).
332
IICC12
P-599
Synthesis and Characterization of a Binuclear Iron(III) Complex of an Aminophenol
derivative as Model for Non-heme Iron Active Sites
I. Saberikia, E. Safaei*
Institute for Advanced Studies in Basic Sciences (IASBS), 45195, Zanjan , Iran
The non-heme mono and di-iron active sites are found in a wide range of enzymes which perform
different biological functions requiring dioxygen. Tyrosine residue and subsequently tyrosyl radicals
were found to play important roles in some of the non-heme iron metalloenzymes e.g.
ribonucleotide reductase R2 that is responsible for O2 activation. The active sites of these enzymes
contains an oxo(hydroxo) bridged binuclear iron(III), tyrosine and histidine amino acids. In this
work, a binuclear iron(III) complex of a new pentadentate aminoethanol derivative of aminophenol
ligand with an N2O3 donor set has been synthesized as simple molecular model for non-heme diiron enzymes without interference of amino acid residues. This complex has been characterized by
IR, UV-Vis spectroscopic techniques, single crystal X-ray diffraction and magnetic susceptibility
studies. X-ray analysis revealed a binuclear complex in which Fe (III) centers have been surrounded
by two phenolate and one hydroxyl oxygen atoms, and two amine nitrogens of ligand. Both Fe (III)
atoms are held together by two mentioned hydroxyl bridges. The variable temperature magnetic
susceptibility indicates antiferromagnetic coupling between iron centers. This complex was
electrochemically oxidized to produce phenoxyl radical as model for tyrosyl radical in enzyme.
Keywords: Aminophenol, Non-heme, Ribonucleotide reductase, Model Complex
P-600
Synthesis and spectral characterization of some new azo dyes and azo metal complexes
with Co+2,Ni+2 ,Cu+2 and Cr+3 derived from 4, 6-dihydroxy pyrimidine
a
H. Yousefia, M. R. Yazdanbakhsha *, H. Pouramira, A. Dadashia
Department of Chemistry, Faculty of Sciences, University of Guilan, Rasht, Iran
Some pyrimidine derivatives possess biological and pharmacological properties. Interesting activities
of reported pyrimidines have stimulated chemists to develop the chemistry of these compounds.
Some azo pyrimidine derivatives also find application in dyes and complexes. Metal complexes of
monoazo compounds are principally useful as trivalent chromium and cobalt complexes for dyeing
of protein and polyamide fibers. Metal-complex dyes are very versatile in terms of applications.
Virtually all substrates, apart from a few synthetic fibers, can be dyed and printed with this class of
dyes. Countless shades from greenish yellow to deep black can be generated, depending upon the
metal, the dye ligands, and the combination of dye ligands in mixed complex dyes. In commercial
terms the most important cheated metals are chromium, cobalt, copper, iron, and nickel. The
resulting dyeing of chromium and cobalt complex dyes is in general dull but exhibits a high
standard of fastness, particularly light fastness. In this research a number of new azo dyes were
synthesized. These synthesis were started by coupling 4,6- dihydroxy pyrimidine with diazotized
heterocyclic aromatic and nonheterocyclic aromatic amines. In other effort, we used one of the
synthesized dyes and also 4, 6-dihydroxy pyrimidine as ligands for preparing some new metal
complexes. The structure of all synthesized compounds was confirmed by IR, 1H NMR, 13C NMR,
UV-Vis, Mass Spectroscopy and elemental analysis.
Keywords: Azo dyes, Azo metal complex, 4, 6-dihydroxy pyrimidine
IICC12
333
P-601
Tridentate [NNO] Type Schiff Base Ligand (Bzabza): Synthesis, Characterization and
Crystal structure of Cu(Bzabza)(CH3COO)
Roghayeh Sadeghi Eramia, Mehdi Amirnasr*a, Soraia Meghdadia, Vratislav Langerb
Environmental Inorganic Chemistry, Department of Chemical and Biological Engineering, Chalmers
University of Technology, SE-412 96 Gothenburg, Sweden
a
b
Schiff bases complexes have remained an important and popular area of research due to their
simple synthesis, versatility, and diverse range of applications . Coordination chemistry of copper
complexes is a subject of continuing importance in connection with the structures and the
reactivities of copper-containing metalloproteins. Many reports are available for the preparation and
properties of model copper complexes which mimic copper-containing metalloproteins such as
hemocyanine and tyrosinase. Two noticeable properties of copper proteins are an intense
absorption band near 600 nm and relatively high copper(II)/copper(I) reduction potentials . In this
study, the copper complex of benzoylacetone-2- aminobenzylamine (Bzabza), [Cu(Bzabza)(OAc)]
have been synthesized and characterized by elemental analyses, IR, UV–Vis, and X-ray
Crystallography. A perspective drawing of the molecule, with crystallographic numbering of the
atoms, is shown in Fig.1 The CuII ion is coordinated to Bzabza Schiff base ligand and one oxygen
molecule of acetate and displays a distorted square-planar coordination geometry with P42/n space
symmetry. The H-bonding interactions of the amine hydrogen and the non-bonding interactions of
phenyl groups in the Schiff base play important role for the structural variations.
Keywords: Cooper(ll)acetate, Schiff base, X-ray crystal structure.
P-602
Effect of Nickel loading in Activity of Fe-Mo-Ni catalyst over ZMS-5 for Oxidation of
Methanol to Formaldehyde
R.Sadeghi a, M. H. Peyrovi a,*,T. Hamoulea and B. Saboura
Department of chemistry, University of shahid beheshti, Tehran, Iran
( e-mail: [email protected])
Department of Chemistry, Faculty of Science, Shahid Beheshti University, Evin, Tehran, Iran
a
Formaldehyde is one of the most important basic chemicals it is an important precursor to many
other chemical compounds, especially for polymers. Two processes are commonly employed for
formaldehyde manufacture: 1) Dehydrogenation of methanol rich air mixture over silver catalysts,
2) Oxidation of methanol over iron molybdate (Mo-Fe-O) based catalysts. Due to weak resistance to
mechanical abrasion, unsupported Mo-Fe-O catalysts cannot be used in fluidized bed reactors. In
this work oxidation of Methanol to formaldehyde over modified Fe-Mo-Ni catalysts was studied
experimentally in a continuous fixed bed reactor over a wide range of reaction conditions. In order
to observe the effect of Ni on the catalytic functionality, the reaction was carried out over catalysts
by various Ni contents. Results show that activity and selectivity of catalysts are dependent on
reaction parameters. For example catalytic functionalities vary in linear manner with rise
temperature.
Keywords: Formaldehyde; Iron-Molybdate-Nickel; Methanol; Activity; Selective Oxidation
334
IICC12
P-603
Potentiometric study of metal ion complexes with 5-methoxy salpn and either ATP or
ADP
a
S. Sadeghia, A. Shokrollahib*, M. Khajehzadeb M. Montazerozohorib
b
Department of Chemistry, University of yasouj, yasouj 75918-74831, Iran
Some of Schiff base derivatives or their metal complexes show antibacterial activity, effective
antifungal, anti-HIV and antiviral activity. On the other hand adenosine triphosphate (ATP) and
adenosine diphosphate (ADP) are important enzymatic compounds in the life sciences. These
compounds are the major source of energy for cellular reactions. The binding of anions by organic
ligands, has been much less investigated than cation complexation, although a multitude of new
structures and properties may be expected in view of the role played by anionic species in chemical
as well as in biological processes. There is no report on the interaction between Schiff bases and
ATP or ADP as important compounds in biological systems. In this work potentiometric equilibrium
studies were carried out to determine the degree of binding of ATP and ADP with various
protonated forms of Schiff base as a template of this class of compounds, with its Cu2+, Co2+, Zn2+
complexes and with the protonated chelates in ternary systems.
Keywords: potentiometric study, ATP, ADP
P-604
Synthesis and Characterization of Mono- and Binuclear Iron (III) Complexes of
Aminophenol Ligands as Models for non-heme Iron Metalloenzymes
E. Safaei*, H. Sheykhi
Mono- and binuclear non-heme iron centers are present in some of the metalloproteins that
perform important biological functions involving dioxygen. The non-heme iron proteins catalyze the
oxidative cleavage of aromatic environmental pollutants. In the present work, a mononuclear
iron(III) complex of aminophenol (LtrsFe) and two binuclear complexes of hydroxy (L2OHFe2) and
methoxy (L2OMeFe2) derivatives of mentioned ligand have been synthesized and characterized by
spectroscopic techniques, X-ray and magnetic susceptibility studies. X-ray analysis reveals that
LtrsFe has a distorted trigonal bipyramid geometry in which three phenolate oxygen atoms, an
amine nitrogen and a methanol molecule have been coordinated to the iron atom. Both L2OHFe2 and
L2OMeFe2 have dimmer structures in which every iron atom has been surrounded by an amine nitrogen,
two phenolate groups and hydroxyl oxygen atoms of ligand in the former or solvent in the latter
case. Hydroxyl groups act as µ-bridging ligands for two iron centers. The magnetic susceptibility
indicates a paramagnetic high spin iron(III) in LtrsFe and antiferromagnetic coupling of iron centers
in another complexes. It has been shown that electrochemical oxidations of all complexes are
ligand-centered due to the formation of the phenoxyl radicals.
Keywords: Catechol dioxygenases, Non-heme, Model complex, Iron complexes
IICC12
335
P-605
Synthesis ,spectroscopic characterization and computational study of some di and
triorganotin ditiocarboxylates
Mojdeh Safaria,*, Mohammad Yousefia, Maryam Bikhofa
Azad university , Shahre-Rey branch, Tehran, Iran
( [email protected])
Organotin(IV) dithiocarboxylates are the subject of intensive investigations due to their structural
diversity, anti tumor activity and biological applications. The coordination with the Sn atom depends
not only on factors such as structure of the organic groups, but also whether the 1,1-dithiolate
moiety behaves as monodentate or bidentate. Three new di and triorganotin(IV) dithiocarboxylates
with general formula R3SnCL and R2SnCl2 where R=methyl (1), butyl (2), phenyl (3) and
L=dithiomorpholincarbamate, have been synthesized and characterized by elemental analysis ,FTIR, multinuclear NMR (1H,13C,119Sn) . The ligand salt was prepared by dropwise addition of CS2(in
excess) to morpholine followed by stirring for 4 h at 0˚C. The white product was filtered off and
was washed with diethyl ether. This mechanism has been proposed on the nucleophilic attack of
morpholine on carbon disulfide gave morpholine-1-carbodithioic acid as intermediate which
undergoes acid-base reaction with unreacted morpholine to gave the ligand salt. R3SnCl and L-salt
were mixed in methanol and the mixture was refluxed for 6 h with constant stirring. Diorganotin
complexes were prepared in the same way,the only difference being ratio,which is 1:2 . In
continuation of our work the computational study was carried out in order to predict their structural
parameters and to compare the calculated results with the experimental results. Spectroscopic
exploration confirmed penta and hexa-coordinate geometry for compounds.
Keywords: organotin(IV), Dithiomorpholincarbamate, Spectroscopy, Synthesis
P-606
The Reaction of Iron porphyrin with a Series of Lewis bases: piperidine, pipyrazin and
Pyrrolidine
a
J. Saffaria, M. Khorasani-Motlagha,*and M. Noroozifara
The properties, structures, and reaction mechanisms and their interrelation of porphyrin complexes
have been the subject of considerable interest recently in light of their possible relevance as models
for the structure function relationships of the important class of iron hemoproteins. A great number
of experimental results have been reported over the past decades concerning the axial ligation
properties of metalloporphyrins with S, O, P and N bases. In this study the equilibrium constants for
addition of some Lewis bases, (piperidine, pipyrazin and pyrrolidine), as axial ligands, to OEPFeClO4
(OEP =octaethylporphyrin) in CH2Cl2, have been measured by UV-Visible absorption titrations. The
equilibria observed are: OEPFeClO4 + B ' OEPFeBClO4 (K1), and OEPFeBClO4 + B ' OEPFeB2 +ClO4 ̄
(K2), (K1<K2). The Soret and Q bands of the complexes were red-shifted, and the equilibria
constants with piperidine and pyrrolidine titration have similar magnitude. This titration shows
isobestic points and the data can be fitted the equation: ln(A -Ao/Ac-A)=n ln[L]+lnK, where A0,
initial absorbance; Af final absorbance; A, absorbance at a specific [L]; and K is the binding
constant. Our results show that the binding process for these ligands to Fe(OEP) are similar and
lead to a better understanding of the complex electronic interactions between the metal and the
axial ligands.
Keywords: Iron porphyrin, Axial ligand, Titration, Equilibrium constant.
336
IICC12
P-607
Theoretical investigation for prediction the stability of two crystalline form of
OEPFeDicydH
a
J. Saffaria, b, M. Khorasani-Motlaghb,*and M. Noroozifarb
b
Department of Chemistry, Islamic Azad University, Zahedan Branch
Porphines play an important role in a number of fundamental biological processes, like
monooxygenases, biological redox reactions, and oxygen transport processes. These compounds
have attracted the attention of many quantum chemists, as well as other chemists and biochemists,
and have been vastly studied theoretically for the last three decades. Advances in computational
sciences have allowed theoreticians to model increasingly complex molecules and these results,
now fully complement the more traditional studies of synthetic chemists. In this work we have used
single-point calculation on two crystalline form of OEPFeDicydH and then used theoretical methods
to investigate geometry, energetics, and stability of these porphine molecules. All calculations have
been carried out by using Gaussian-98 (R-A.9) software. In order to obtain local minima geometries
of free porphine molecule, two different methods namely HF and B3LYP have been employed with
three usual basis sets: 3-21G, 6-31G, and 6- 31G (d). The final results also have been compared
with together and other theoretical studies, and a good correspondence has been detected. By
taking a look at results of the calculations, it is clear that B3LYP method results are closer to the
experimental data such as X-Ray data.
Keywords: Iron porphyrin, Axial ligand, HF, B3LYP.
P-608
Synthesis and characterization of copper(II) and cobalt(II) complexes with imidazo
[4,5-f]1,10-phenanthrolin derivatives
LotfAli Saghatforousha,*, Ghasem Marandia, Soheila Sanatyb
Department of Chemistry,payame Noor University, khoy,Iran
E-mail:[email protected]
b
Department of chemistry ,Payam Noor University-Tabriz Center,Tabriz,Iran
a
The Schiff bases are widely employed as ligands in coordination chemistry. These ligands are
readily available, versatile and, depending on the nature of the starting materials (primary amines
and carbonyl precursors), they exhibit various denticities and functionalities. Two imidazo
containing Schiff base ligands, TIP (TIP=2-(thiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline
and FIP (FIP=2-(Furan-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, were synthesized
by a
multicomponent condensation of 1,10-phenanthroline-5,6-dione and aldehydes in the presence of
Ammonium acetate and triethyl amine. The copper (II) and cobalt (II) complexes of these ligands
were prepared by the reaction of equimolar amounts of the ligands and metal salts [3-4]. The
synthesized compounds were characterized by elemental analyses, IR, 1H-, 13C-NMR, mass and UvVis spectroscopy.
Keywords: Copper (II) complex, Cobalt (II) complex, Imidazo[4,5-f][1,10]-phenanthroline, Schiff
base.
IICC12
337
P-609
Synthesis of Copper(II) and nickel(II) Schiff base complexes: Study of their
Spectroscopic and Antibacterial Properties
L.A. Saghatforoush*, R. Mehdizadeh
Department of Chemistry, Payame Noor university, khoy, Iran,
1,10-Phenanthroline-5,6-dione is a versatile ligand for the assembly of metal organic materials. It
can be used directly as a bis-chelating ligand, and be prepared starting from an already complexed
phenantroline. This work deals with the synthesis and characteristics of new copper (II) and
nickel(II) complexes of Schiff base ligand (4,5,9,13,14-pentaaza-benzo[b] triphenylen (L)). The
antibacterial activity of Schiff base and its complexes are reported against the three Gram-positive
bacteria: Streptococcus pyogenes (RTCC 1949), Staphylococcus aureus (RTCC 1113) and Bacillus
anthracis (RTCC 1036) and also against the three Gram-negative bacteria: Klebsiella pneumonia
(RTCC 1249) and Pseudomonas aeruginosa (RTCC 1541), Escherichia coli (RTCC 1330). To an
ethanol solution of meal salt (copper or nickel nitrate) an ethanol solution of L was added. The
resulting solution was refluxed. The product was removed by filtration, washed with cooled absolute
ethanol and recrystalized from methanol and dried in vacuo. The ligand and its metal complexes
have been characterized by CHN, FT-IR, 1H, 13CNMR, UV–Vis, (TGA, DSC) and conductivity
measurements. Ni (II) and Cu (II) form complexes of composition [Cu(L)2NO3]NO3, [Ni(L)2(NO3)2].
The results clearly demonstrate that L is bidentate. The Ni complex shows better activity against all
tested bacteria in comparising with ligand.
Keywords: Schiff base, Copper (II), Nickel (II), Antibacterial, Spectral studies.
P-610
Synthesis and structural characterization of new Cd(II) complexes with
4′–(4–methyl phenyl)-2,2′:6′,2″-terpyridine ligand
L.A. Saghatforoush*, f. shakarami
Department of Chemistry, Payame Noor University, khoy, Iran,
Terpyridene ligands have been known for nearly a century as effective complexing agents for wide
range of metal ions. Tow cadmium (II) complexes of the ligand 4′–(4–methyl phenyl)-2,2′:6′,2″terpyridine in the presences of different counter ions (N‫־‬3 and ClO4-) with mole ratio 1:1:2 from the
metal ion, terpyridine ligand and anion have been synthesized as single crystals by the branched
tube method at 60°C. The obtained complexes have been characterized by common physical
methods and structurally analyzed by X-ray single–crystal diffraction. These compounds formulated
as [Cd2(MPhtpy)2(N3)4] (1), [Cd(MPhtpy)2](ClO4)2 (2). The single crystal X-ray analyses show that
both complexes crystallize in monoclinic space group P21/n. The asymmetric unit of (1) contains
two independent molecules. Each centrosymmetric dimmer consists of Cd(II) ions linked by two
end-on bridging azide groups. The other two azides act as terminal ligands. Each cadmium atom is
located in a distorted octahedral coordination environment surrounded by six nitrogen atoms, three
from the tridentate ligand moiety, two from end-on µ2-bridges azido groups and the last one from
the one terminal azido ion. There are one Cd(II) atom, two Mephtepy and two ClO4- anion in the
asymmetric unit of (2). Cd(II) center in (2) adopts a six-coordinate structure by coordinating to six
nitrogen atoms from two tridentate domain of Mephtpy ligands.
Keywords: Cd(II), 2,2′:6′,2″-terpyridine, crystal structure.
338
IICC12
P-611
Synthesis and characterization of Cobalt (III) complexes containing N2O2 donor
tetradentate Schiff-base ligand N,N-bis (salicylidene)-1,3-diaminopropane(
salpn) with anionic and neutral ligands:
a
F.Saleha,*,S.J.Moafia
Schiff base ligands prepare by condensation reaction between simple amines and formyl functional
groups. The resulted imine reacts with metal ions by nitrogen lone pair electrons.These components
have been utilized as artificial oxygen carriers. Characterization the linked molecular oxygen to the
transition metals can be investigated specifically by EPR spectroscopy.In our research, first, the
tetradentate Schiff-base N,N-bis (salicylidene)-1,3-diaminopropane( salpn) ligand was prepared by
addition of 1 equivalent amine, to 2 equivalent salicylaldehyde in ethanolic solution. The resulted
solution was refluxed for 1 hour, when yellow precipitate was formed .The mentioned Schiff-base
ligand refluxed with Cobalt (II) ion and NaoH under Nitrogen atmosphere. The desired [CoII (salpn)

In the name of God the Merciful the Compassionate

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