(E)-1,5- diphenylcarbazone uranyl acetate (VI)
Transcription
(E)-1,5- diphenylcarbazone uranyl acetate (VI)
International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok 1 H- NMR, Electronic properties and conductivity studies of (E)-1,5diphenylcarbazone uranyl acetate (VI) P P P P [{(Ar)NNHCONN(Ar) 2}UO2(Ac)(EtOH)] (Ar = C6H5, acc = CH3COO ) Complex R R R R R R R R R R Salem El-t. Ashoor 1B Different optical conductivity enhancement (OCE) protocols to eliminate charging during ultra low energy SIMS profiling of semiconductor and semi-insulating materials using interaction between the material and the primary ion beam by some cases (Si1-xGex, phosphorus implanted silicon) was archived by Morris et al.7 Again conductivity of ZnCoO diluted magnetic semiconductor was examined in room temperature ferromagnetic semiconductor, Cu-codoped ZnCoO film are obtained by sol-gel method. By hall-effect measurement a p-type conductivity was observed for the Cucodoped films, the hole concentration increases with the increase in Cu concentraton.8 The conductivity of the glasses have been studied over ranges of compositions and frequency by Kanchan in 2009 and his group9 using transport properties and relaxation studies in BaO substituted Ag 2 O-V 2 O 5 -TeO 2 glass system and how the increases conductivity while activation energy decreases. Electronic structure of layered uranium compounds from photoemission spectroscopy was showen tetragonal compounds and anti-ferromagnet and ferromagnet and also they observed intriguing electronic structure for the complexes were synthesized by Arko and his group.10 Energetics of intrinsic point defects in uranium dioxide from electronic structure calculations, the computational approach integrates high accuracy initio electronic structure calculation and thermodynamic analysis supported by experimental data 11 Abstract— A range of new compounds such (E)-1,5diphenylcarbazone uranyl acetate (VI) [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(EtOH)] (Ar = C 6 H 5 , acac = CH 3 COO ) complex counting the chelating tertaamine and oxygen has been prepared, and structurally characterized in several cases. Well-defined (E)-1,5-diphenylcarbazoneurinailacetate [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] Ar = C 6 H 5 , acac = CH 3 COO) (Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 , acac = CH 3 COO ) was obtained by stoichiometric addition of [(Ar) NHNHCONN(Ar) 2 } 2 } (Ar = C 6 H 5 ) and {UO 2 (acac) 2 } in ethanol at reflex temperature. HNMR, IR, CHN, Electronic properties and conductivity studies have been obtained for this compound. Electronic Properties by using hyperchem program study has been improved for this compound such bond distance and then this compound was defining as electric conductivity also did prove to be useful use for conductively compound. P P P P P R Keywords— Acetate, (E)-1,5-Diphenylcarbazone, Conductivity, Electronic Properties And, Tertaamine Uranyl. I. P INTRODUCTION T HE Interest area, Schiff bases ligands have been focused in the last ten years ago specially with transition metal to forward complexes, due multiple implication.1-5 Oxygen and nitrogen as tetra-dentate attached to cobalt acetate has been reported by Aurel et al.6 and catalytic activity leads to the obtention of benzoquinone and diphenoquinone products. Different optical conductivity enhancement (OCE) protocols to eliminate charging during ultra low energy SIMS profiling of semiconductor and semi-insulating materials using interaction between the material and the primary ion beam by some cases (Si1-xGex, phosphorus implanted silicon) was archived by Morris et al.7 Again conductivity of ZnCoO diluted magnetic semiconductor was examined in room R R R R R R R P 4B P P II. EXPERIMENTAL A. Syntheses of (E)-1,5-diphenylcarbazone uranyl acetate (Ar = (VI) [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(EtOH)] C 6 H 5 , acac = CH 3 COO ):R R R R R R R R R R A solution of uranyl acetate (VI) ( 280 mg, 1.179 mmol) in ethanol (30 ml) and then (E)-1,5diphenylcarbazoneurinailacetate ( 280 mg, 1.179 mmol mol ) in (40 ml) of ethanol was added drops at room temperature Salem El-Tuhami ASHOOR, Chemistry department Faculty Science, Misurata University, Misurat-Libya (corresponding author to provide: ;fax: +218-512623191; e-mail: [email protected] or [email protected]). 133 International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok and after 15 minutes in room temperature stirring the temperature was arise to reflux for 5 hours. During that time the colure was changed from red-brown to pink. The mixture was filtered and the solution was reduced to volume (20 ml) and after that was stored at low room temperature for 24 hours. The dark brown-pink crystal of the [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 , acac = CH 3 COO ) in yield ( 550 mg, 0.990 mmol, 83%) (Scheme 1). Anal calcd for C 14 H 26 N 4 O 5 U, C: 31.8, H: 3.55, N: 9.89. Found. C: 32.23, H: 3.98, N: 9.57. Mp = 146-147 oC In solution 3 undergoes dynamic behaviour as shown in its room temperature 1H NMR spectrum in chloroform-d. All peaks that we expected were arising from the CH 3 CH 2 OH group is resolvable 3.7 ppm (q, 2H, CH 2 ), 1.1 ppm (t, suggesting that is 3H,CH 3 ), 2.2 ppm (S, H, OH) uncoordinated to the urinal centre. Again the peak of H ( NHCO-R) is celery appear at ( = 8.10 p pm) that come across with our experimental just one acetyl acetate was eliminated from the metal centre. Also disappear the singlet peak that especially for (s, H, ArNHN) which suggesting that is one mole of acetyl acetate was eliminate from metal centre. Other peaks such aromatics system were appear at (δ = 6.90, ppm) (m, 6H, C 6 H 5 ) and (δ = 7.15 ppm) (m, 6H, C 6 H 5 ). This complex 3 comparable to other published dioxouranium (VI) and uranyl ion with aminoalcoholbis(phenolate) complexs.12, Scheme 1 (E)-1,5-diphenylcarbazone uranyl acetate (VI) H N N H3COO U O O O N 13 N B. UV- Visible Study : 3 Ref. 5h EtOH The electronic spectrum of 3 shows four picks. Strong pick at 229 nm which in frequency 43668 cm-1, madam pick at 293 nm which is in 34129 cm-1, these are due to intraligand π →π* and n→ π* and with other picks at 472 and 648 nm in frequency 21186 cm-1 and 15432 cm-1 these are consists for complex exhibit a pair of bands appearing in publication the region 20000 – 14300 cm-1. 14, 15 O HN HN N N [UO2(CH3COO)2] 1 2 (E)-1,5-diphenylcarbazone Fig. 1 Scheme 1 B. Spectroscopic Techniques: C. Electronic and structural properties Electronic spectra were recorded at room temperature on UV-Vis spectrophotometer mini 1240- Shimadzu. The convergence is set to 0.001 kcal molK1. The electronic properties of (E)-1,5-diphenylcarbazone uranyl acetate (VI) [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 , acac = CH 3 COO ) 3 showen in table 1. 1 H NMR spectra of 3 was acquired at El-fatah universityLibya on a Bruker Spectrospin AG 300DPX and operating at 300.13 MHz for 1H measurements. Chemical shifts are reported in ppm and referenced to the solvent peaks. Coupling constants are quoted in Hertz (Hz). TABLE 1 : ELECTRONIC PROPERTIES OF 3 : Geometry optimization of the studied molecules was done by performing the semi-empirical molecular orbital theory at the level PM3 using the restricted Hartree–Fock (RHF) procedure bye using Hyperchem program version 7.5 running on a Windows XP workstation with a Pentium IV PC. The Polak– Ribier algorithm was used for the optimization. Conductivity measurement was carryout in glass device and photometer measurements. Elemental analyses for 3 were carried out by Asuete University- Egypt. Total Energy -29351.70313 (kcal/mol) Total Dipole Moment 78.92D Energy Symmetry (CS) -29351.702203 (kcal/mol Orbital (HOMO) Energy Symmetry 25.66085 er Symmetry 38A` C. Reagents and Materials: UO 2 (acac) 2 and (E)-1,5-diphenylcarbazone were purchased from Aldrich . Ethanol was order from from Acros. The structural properties of 3 to conform optimized structure shown in fig. 2 III. RESULTS AND DISCUSSIONS A. 1H NMR Study : 134 International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok even after reflex 5 hour. They did prove to be useful metathesis reagents for introducing the chelating amides of the ligand to uranyl metal centre. Also one mole of the solvent was not co-ordinate with ion metal of the complexes unusual saturation state as shown by NMR as free. Also the geometry optimization of the studied molecules were done by performing the semi-empirical molecular orbital theory at the level PM3 using the restricted Hartree–Fock (RHF) procedure and showed the high energy of this compound. Conductivity behavior of the 3 was found within the range of semiconductors. Fig. 2 The optimized structure Appendix 1 D. Conductivity study : Conductivity behavior of the 3 was followed the Arrhenius behavior and the activation energy can be calculated using different temperatures. The conductivity of this compound 3 has been explaind in term of the following Eq. σ = 1/ρ = Ω cm-1 were ρ = R A/L and A = π r2 A = 3.14 x (0.25)2 = zz → R = V/I = 0.9998v/ 1.08717 x 10-7 A = dd P = dd zz/0.1 Were: ρ = specific resistance & A = surface area & R = resistance & V = voltage & I = current intensity The value of conductivity was shown to be writhen the range of semiconductors values (1.5 x 106 ) Ω cm. The following graph explains the relation between current and voltage (Appendix 1). The slope equal to resistance, from the obtained the resistance the resistively was calculated according to the above mentioned equations A(X) B(Y) A(X) B(Y) 1 2.7 E-6 5.5 1.42 E-5 1.5 3.8 E-6 6 1.56 E-5 2 5.2 E-6 6.5 1.68 E-5 2.5 6.4 E-6 7 1.80 E-5 3 7.8 E-6 7.5 1.93 E-5 3.5 9.0 E-6 8 2.03 E-5 4 1.04 E-5 8.5 2.19 E-5 4.5 1.15 E-5 9 2.32 E-5 5 1.29 E-5 9.5 2.46 E-5 10 2.59 E-5 ACKNOWLEDGMENT This study was done in chemistry department science faculty Misurata university witch we are extremely grateful to the department and university for to given the chance. 0.000030 SEAII. 5 Data1B (SEAII. 5) 0.000025 Current A 0.000020 REFERENCES 0.000015 [1] [2] [3] P. A. Vigato, S. Tamburinii, Coord. Chem. Rev.248(2004)1717. J. P. Collman, L. Zeng, J. I. Brauman. Inorg. Chem. 43(2004) 2672. T. Achard, Y. N. Belokon, J. A. Fuentes. M. North, T. Parsons, Tetrahedron 60 (2004)5919. [4] K. P. Bryliakov, E. P. 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Chem. 36 (1997) 2944. 0.000010 0.000005 0.000000 0 2 4 6 8 10 Voltage V Fig. 3 Graph between current and voltage Conductivity arises mainly while the activation energy increase, the conductivity is due the electronic transfer between the aromatic system and nitrogen attached the aromatic and then to metal centre (delocalization electron). The conductivity of 3 has been measured in the voltage range 1 to 10 V. It is found to follow the Jonscher`s power law. IV. CONCLUSIONS The chemistry presented in this paper shows that not only chelating with one amides of with U(VI) are accessible, but that simple acetylacetate still co-ordinate with metal centre [15] 135 A. T. Mubarak, Spectrochimica Acta Part A 65 (2006) 1197-1207.