48 Inorganic Discussion Weekend 48 Rencontres

Transcription

48th Inorganic Discussion Weekend
48e Rencontres inorganiques
November 6-8, 2015
Royal Military College of Canada
Itinerary
Friday, November 6th
1900-2200
Air Liquide Mixer
Saturday, November 7th
0800-0820
Registration and coffee
0820-0830
Opening remarks
0830-0930
Plenary Lecture
0930-1000
Coffee break
1000-1120
Oral sessions 1-2
1130-1230
Lunch
1230-1330
Poster set-up/exhibition
1340-1440
Oral sessions 3-4
1440-1500
Coffee Break
1500-1620
Oral sessions 5-6
1630-1830
Poster session
1900-2355
Banquet
Sunday, November 8th
0800-0830
Coffee
0830-1010
Oral sessions 7-8
1010-1030
Coffee break
1030-1130
Oral sessions 9-10
1145-1245
Plenary Lecture 2
1245-1300
Awards and closing ceremonies
Tir Nan Og
Baronial Hall
Currie Hall
Currie Hall
Massey Hallway
Massey 7 and 15
Cadet Dining Hall
Massey 7 and 15
Massey Hallway
Massey 7 and 15
New Gym
Yeo Hall Cadet Mess
Massey Hallway
Massey 7 and 15
Massey Hallway
Massey 7 and 15
Currie Hall
Currie Hall
Bus Schedule:
There will be free shuttle buses between the Holiday Inn and campus at the following times:
Saturday between 0730-0800 and 2100-2355
Sunday between 0730-0800 and at 1300
Parking:
If you are bringing your own car, there will be free parking in the Sawyer Parking Lot and you will be
issued a parking pass upon coming through the Gate House.
Gold Sponsors
Silver Sponsors
Bronze Sponsors
Air Liquide Mixer
Time:
start at 1900 (Registration ends at 2200)
Where:
Tir Nan Og
200 Ontario St, Kingston, ON K7L 2Y9
(613) 544-7474
https://www.facebook.com/kingston.tirnanog
Musical Entertainment: RMC’s own
Tir Nan Og is also open for dinner and offers great pub-style food.
Gate house
P
Massey Building – Oral sessions
(Rooms M7 and M15)
Currie Building – Plenary Lectures
(Currie and Baronial Hall)
Yeo Hall – Lunch, Poster session, Banquet
(Cadet Dining Hall, Mess, and New Gym)
Program of events
Saturday, November 7th, 2015
08:00-08:20
Registration and Coffee (Baronial Hall)
08:20-08:30
Opening Remarks: Dr. Gord Simmons, Dean of Science, RMC (Currie Hall)
08:30-09:30
Plenary Lecture: Dr. Ken J. Reimer, Royal Military College (Currie Hall)
09:30-10:00
Coffee Break (Massey Hallway – Sponsored by New Journal of Chemistry)
10:00-11:20
Oral session 1
Massey 7
10:00
10:20
10:40
Massey 15
O1 1,2,4,6-Thiatriazinyl Radicals and Dimers:
Structural and Electronic Tuning through
Heteroaromatic Substituent Modification
O5 New Ruthenium (II) Complex with Pyrazole
Containing Ligand and Its Catalytic Activity in
Transfer Hydrogenation
Nathan J. Yutronkie (University of Ottawa), A.A.
Leitch, J.A. Klein, I. Korobkov, J.L. Brusso
Iryna D. Alshakova (Brock University), G.I.
Nikonov
O2 ‘All three-in-one’: Ferromagnetic Interactions,
Single-Molecule Magnetism and Magnetocaloric
Properties in a New Family of [Cu4Ln] Clusters
O6 Electronic Structure and Bonding in Iron(II) and
Iron(I) Complexes Bearing Bisphosphine Ligands of
Relevance to Iron-Catalyzed C-C Cross-Coupling
Paul Richardson (Brock University), D.I.
Alexandropoulos, L. Cunha-Silva, G. Lorusso, M.
Evangelist, J. Tangi, T.C. Stamatatos
Jared L. Kneebone (University of Rochester), V.E.
Fleischauer, S.L. Daifuku, A.A. Shaps, J.M. Bailey,
T.E. Iannuzzi, M.L. Neidig
O3 Study of a Novel Hepta-Coordinated FeIII
Bimetalic Complex with an Unusual 1,2,4,5Tetrazine-Ring Opening
O7 Aqueous Biphasic Iron-Catalyzed Asymmetric
Transfer Hydrogenation of Ketones
Maykon A. Lemes (University of Ottawa), A.
Pialat, S.N. Steinmann, I. Korobkov, C. Michel, M.
Murugesu
Karl Z. Demmans (University of Toronto), O.W.K.
Ko, R.H. Morris
O4 A Mononuclear Supramolecular Capsule with
Single Molecule Magnet Behaviour
O8 Catalyst Choice in Cross-Metathesis of
Electron-Deficient Olefins: Phosphine-Induced
Catalyst Decomposition
Majeda Al Hareri (Brock University), E. Gavey,
M. Pilkington
Gwendolyn A. Bailey (University of Ottawa), D.E.
Fogg
11:00
11:30-12:30
Lunch (Cadet Dining Hall)
12:30-13:30
RMC Exhibition and Poster Set-up (New Gym)
13:40-14:40
Oral Session 2
Massey 7
13:40
14:00
Massey 15
O9 Synthesis and Characterization of Side-Chain
Boron Difluoride Formazanate Polymers
O12 Towards Carrier-Mediated Water Splitting –
Catalytic Dehydrogenation of Formaldehyde
Samantha Novoa (Western University), J.A.
Paquette, S.M. Barbon, R.R. Maar, J.B. Gilroy
Nicholas Alderman (University of Ottawa), C.
Viasus, J. Sommers, V. Peneau, L. Hull, S. Alshehri,
S. Gambarotta
O10 Alkyl-Functionalization of 3,5-Bis-(2-Pyridyl)1,2,4,6-Thiatriazine Complexes
O13 Catalytic Hydrogenation of CO2 to Formamide
using Non-precious Metal Catalysts
Elizabeth Kleisath (University of Ottawa), N.
Yutronkie, I. Korobkov, B. Gabidullin, J. Brusso
Mohammad A. Affan (Queen’s University), P.G.
Jessop
O11 Towards Highly Conjugated and Functional
Materials: the Quest for Polyazaborinines
O14 Ruthenium and Iridium Complexes of PolyPyridine Ligands as Homogeneous Catalysts for the
Hydrodeoxygenation of Biomass-Derived Substrates
to Value-Added Chemicals
Soren Mellerup (Queen’s University), S. Wang
Elnaz Latifi (University of Guelph), R.J. Sullivan,
T.A. Minard, C.T. Oswin, M. Schlaf
14:20
14:40-15:00
Coffee Break (Massey Hallway – Sponsored by Systems for Research)
15:00-16:20
Oral session 3
Massey 7
15:00
15:20
O15 A Fluorescent Radical-Functionalized PolyAromatic Hydrocarbon Polymer Composite
O19 Synthesis and Coordination of Amidines and
Phosphaamidines Metal Complexes
Mitchell Nascimento (University of Windsor), Y.
Beldjoudi, I. Osorio-Roman, J.M. Rawson
Ramjee Kandel (Queen’s University), K. Huynh, L.
Dalgliesh, R. Wang, P.G. Jessop
O16 Multichromic Supramolecular Dye
Architectures for Advanced Light-Harvesting
Applications
O20 Manganese(II) Dialkyl and Manganese(I) and
(III) Hydride Complexes
Muhammad Yousaf (Ryerson University), B.D.
Koivisto
Jeffrey S. Price (McMaster University), P. Chadha,
D.J.H. Emslie
O17 The Formation of Gold Thiophene Nanoreactor
By Mediating Metal-Polymer Interaction
O21 Nitrene Transfer from Organic Azides
Mediated by Metal Complexes of Bulky oPhenylenediamide Ligand
Vishva Shah (Royal Military College), C.
Malardier-Jugroot, M. Jugroot
Pavel Zatsepin (University of Toronto), T. Janes, D.
Song
O18 Electrochemical Characterizations of UltraStable Self-assembled Monolayers of NHeterocyclic Carbenes on Gold
O22 Solvent Stabilized Dinitrogen Trioxide as a
Laboratory Reagent
Zhe She (University of Toronto Scarborough), M.R.
Narouz, C.A. Smith, C.M. Crudden, J.H. Horton, H.B. Kraatz
Kristopher Rosadiuk (McGill University), D.S.
Bohle
15:40
16:00
Massey 15
16:30-18:30
Poster Session and Exhibition (New Gym)
19:00
Banquet (Yeo Hall)
Sunday, November 8th, 2015
08:00-08:30
Registration and Coffee (Baronial Hall)
08:30-10:10
Oral Session 4
Massey 7
08:30
08:50
09:10
09:30
O23 Evaluation of Anisole-Substituted Boron
Difluoride Formazanate Complexes for
Fluorescence Cell Imaging
O28 Iterative, Protecting Group Free SuzukiMiyaura Coupling of Enantioenriched
Polyboronates
Ryan R. Maar (Western University), S.M. Barbon,
N. Sharma, H. Groom, L.G. Luyt, J.B. Gilroy
C. Ziebenhaus, Jason Rygus (Queen’s University),
K. Ghozati, P.J. Unsworth, S. Voth, Y. Maekawa,
C.M. Crudden, M. Nambo
O24 Pyrido[2,1-a]-isoindole as a Novel Ligand in
Main Group and Transition Metal Chemistry
O29 Chan-Lam Coupling Using a Copper(II)
Complex with a Sulfonated Diketimine Ligand
Sean M. McDonald (Queen’s University), S. Wang
Valérie Hardouin Duparc (Université de
Montréal), F. Schaper
O25 Bis-Carbene-Stabilized Phosphorus Cations
O30 Stable Organopalladium(IV) Aryldiazenido
Complexes
Justin F. Binder (University of Windsor), A.
Swidan, M. Tang, J.H. Nguyen, C.L.B. Macdonald
David Armstrong (University of Toronto
Mississauga), M. Daryanavard, A.J. Lough, U.W.
Fekl
O26 Engineered Designer Monomers: The Path to
Light and Moisture Stable Polystannanes
O31 Selective C(sp2)-O Bond Formation from
Palladium Complexes by Using a Green Oxidant
Jeffrey Pau (Ryerson University), D. Foucher
Ava Behnia (Western University), J.M. Blacquiere,
R.J. Puddephatt
O27 N-Heterocyclic Carbene Stabilized Ag
Nanoparticles
O32 Tuning the Steric and Electronic Properties of
Iron-Based Catalysts Using Modular Phosphine
Moieties
Iraklii I. Ebralidze (University of Toronto
Scarborough), H.-B. Kraatz
Samantha A. M. Smith (University of Toronto),
A.J. Lough, R.H. Morris
09:50
10:10-10:30
Massey 15
Coffee Break (Massey Hallway)
10:30-11:30
Oral session 5
Massey 7
10:30
10:50
11:10
Massey 15
O33 Intercalation of Coordinatively Unsaturated
FeIII Ion within Interpenetrated MOF-5
O36 Ligand Effects in Copper-Catalyzed Aerobic
Oxygenation of Phenols
Rebecca J. Holmberg (University of Ottawa), T.
Burns, S.M. Greer, L. Kobera, S.A. Stoian, I.
Korobkov, S. Hill, D.L. Bryce, T.K. Woo, M.
Murugesu
Laura Andrea Rodríguez Solano (Concordia
University), J.-P. Lumb, X. Ottenwaelder
O34 Towards Modeling the Active Site of
Photosystem II: New Structural Motifs in Mn/Ca
Chemistry from the Use of Salicylhydroxime
O37 1,2-Diphosphonium Dication : A Strong PBased Lewis Acid in Frustrated Lewis Pair
Activations of B-H, Si-H, C-H and H-H Bonds
Alysha A. Alaimo (Brock University), S.J. Teat, G.
Christou, T.C. Stamatatos
Julia M. Bayne (University of Toronto), M.H.
Holthausen, I. Mallov, R. Dobrovetsky, D.W.
Stephan
O35 Synthesis and Biological Activity of FuranContaining Organoruthenium Complexes
O38 Progress in Boro-cation Catalysis for
Hydrofunctionalization
Mohammadmehdi Haghdoost (INRS-Institut), G.
Golbaghi, A. Castonguay
Patrick Eisenberger (Queen’s University), C.M.
Crudden
11:45-12:45
Plenary Lecture: Dr. Daniel J. Mindiola, University of Pennsylvania (Currie Hall)
12:45-13:00
Closing Ceremonies and Awards (Currie Hall)
Dr. K.J. Reimer
Emeritus Professor
Department of Chemistry and Chemical Engineering, Royal Military College of Canada
Ken Reimer received his BSc (1969) and MSc (1971) degrees from the
University of Calgary; the latter dealing with tungsten and molybdenum
complexes and his PhD (1975) from the University of Western Ontario in
organometallic synthesis. He then studied bioinorganic chemistry as a Killam
Postdoctoral Fellow at the University of British Columbia. After teaching briefly
at the University of Guelph he was appointed as an Assistant Professor at Royal
Roads Military College in Victoria, B.C., reaching the rank of Professor before
being transferred to the Royal Military College of Canada in 1995. He also holds
a cross-appointment to Queen’s University School of Environmental Studies.
Upon his retirement from RMC in 2014, Dr. Reimer was appointed Emeritus
Professor and he still maintains an active research program.
Starting with a background in classical inorganic chemistry, Ken became very interested in
interdisciplinary research. This led to a focus on arsenic in the environment and included numerous
sampling programs in the coastal waters of B.C. to examine the effect of mine waste disposal.
Environmental risk assessment was just beginning and found application interpreting the results of these
investigations that had an applied and public component. Ken’s group expanded to include biologists and
oceanographers as well as chemists and he extended his collaboration with researchers in several other
disciplines. In 1989, Dr. Reimer founded, and for the next 25 years was Director of, the Environmental
Sciences Group (ESG) a multidisciplinary team (of 60 -100 people) that conducted basic and applied
environmental research all over the world. ESG was the scientific authority for the Distant Early Warning
Line cleanup – one of Canada’s largest remediation projects. It involved some of the first environmental
site assessments in Canada’s Arctic; the design of the cleanup protocol; numerous consultations with
Inuit; and oversight of the actual remediation itself. This is just one of the hundreds of projects that
typically involved remote locations, novel applications of human health and ecological risk assessment,
actual environmental cleanups and extensive interactions with aboriginal communities. Arsenic continued
to be a basic research focus but the applied work brought interest in a diverse range of contaminants
including persistent organic pollutants, chromium, lead, and cadmium.
Dr. Reimer’s creation of the ESG and its successful involvement with environmental restoration was
rewarded with two National Defence Deputy Minister Commendation Awards in 1992 and 2006. He has
also received the Chemical Institute of Canada’s Environmental Improvement Award and the RMC
Cowan Prize for Excellence in Research. Ken has always been committed to making the results of his
work meaningful to stakeholders and for that reason he is particularly proud of a Real Property Institute
of Canada Award of Excellence in the Field of Contaminated Sites entitled ‘Scientists and Inuit - A Long
Term Partnership’ and a Parks Canada CEO Award of Excellence ‘for an extraordinary contribution in
engaging partnerships with the Inuvialuit. Ken is a Past Chair of the Environment Division of the
Chemical Institute of Canada and is the current Chair of BioAcessibility Research Canada.
Arsenic in the environment, in consumer products, and in you.
Are you at risk?
Ken J. Reimer
Environmental Sciences Group, Department of Chemistry and Chemical Engineering, Royal
Military College of Canada
Email: [email protected]
Recent media articles shock readers with statements like: ‘Arsenic in rice and baby foods’, ‘Arsenic in
Red Wine’, and ‘Arsenic in Apple Juice’ (with the quote: ‘I didn’t know that I was giving poison to my
child’). These attract attention because most people feel that arsenic is synonymous with poison. Arsenic
(as arsenic trioxide) is poisonous and in the Middle Ages was readily available from smelting of gold ore.
It was also colourless, odourless, and tasteless and became so popular that it was known as the ‘King of
Poisons’. Popular writers like Agatha Christie and plays like ‘Arsenic and Old Lace’ further popularized
the notion that arsenic had to be bad.
The real situation is somewhat more complex. For example, when I am asked to comment on those
newspaper headlines I respond with a statement that is counterintuitive to many people. I say ‘of course
we should find arsenic in rice; arsenic is everywhere and it would be more surprising if we did not find it
in our food and drink.’
This talk will describe the ubiquitous presence of arsenic in our environment. Arsenic is present in over
300 minerals and natural weathering processes, together with biogeochemical transformations,
redistribute arsenic into approximately 50 different chemical forms. We know how most of these
transformations take place, including how humans metabolize arsenic, but the production of the one nontoxic arsenical – arsenobetaine, continues to elude us. We also know that high doses of inorganic arsenic
will cause numerous health effects, including cancer, but there is an intense debate about possible health
effects caused by the low dose that we all experience each day. Low dose may be the norm, but there are
situations (such as old mine sites) where arsenic has been redistributed in the environment in very large
amounts. Case studies will be used to examine how chemists can assist in dealing with such problems and
with public concerns regarding arsenophobia.
Dr. Daniel J. Mindiola
Presidential Professor
Department of Chemistry, University of Pennsylvania
Daniel José Mindiola was born in San Cristóbal, Venezuela in 1974. Upon
entering the US with his mother in 1989, Daniel then pursued the remainder of
high school in a small town in mid Michigan, Ovid. Daniel began his college
education at Michigan State University, East Lansing, MI, in 1992. As a
"Spartan", he spent the next three and a half years learning the principles of
inorganic chemistry under the auspices of Professor Kim R. Dunbar. After
obtaining his B.S. degree in chemistry from MSU in 1996, Daniel then attended
the Massachusetts Institute of Technology in Cambridge, MA, under the
guidance of Professor Christopher "Kit" Cummins. In the summer of 2000,
Daniel completed his Ph.D. degree and continued work in small molecule
chemistry as an NIH and FORD post-doctoral fellow in the laboratories of
Professor Gregory L. Hillhouse at the University of Chicago.
After nearly two years at Chicago, Daniel accepted an invitation to join the Chemistry Faculty at Indiana
University in the city of Bloomington, IN (July of 2002). In 2007, he was promoted to Associate
Professor with tenure, and in 2011 to Full Professor. He was the departmental Graduate Advisor from
2008-09 and Chair of Graduate Admissions at IU-Chemistry from 2010-2013. His research work entails
the design and assembly of reactive metal complexes of early metals (in particular 3d metals) and their
role in unusual transformations such as C-H activation and C-N bond cleavage reactions. He is also
interested in novel catalytic processes mediated by reactive complexes containing metal-ligand multiple
bonds.
In the summer of 2013 and after 11 wonderful years in Bloomington, Daniel moved to the University of
Pennsylvania where he holds a Presidential Chair Professorship. In 2014, Daniel was elected as a Fellow
of the Royal Society of Chemistry (FRSC) and is Associate Editor for the ACS journal Organometallics.
He formally was an Associate Editor for Dalton Transactions for 3 years. He has given over 140 lectures
worldwide and published over 140 papers in peer-reviewed journals. Other accolades prior to 2013
include: Fellow, Japan Society for the Promotion of Science; Fellow, Chemistry Research Promotion
Center, National Science Council of Taiwan; College of Natural Science Recent Alumni Award
(Michigan State University); American Chemical Society National Fresenius Award (Phi Lambda
Upsilon); Friedrich Wilhelm Bessel Research Award (Humboldt Foundation); Dalton Lecture Award;
University of California at Berkeley; Camille and Henry Dreyfus New Faculty Award; NSF Presidential
Early Career Award for Scientists and Engineers (PECASE); Alfred P. Sloan Research Fellow; Camille
Dreyfus Teacher-Scholar Award; NSF CAREER Award.
New Developments in Dehydrogenation of Volatile Alkanes with Ti-C
Multiple Bonds.
Daniel J. Mindiola
Department of Chemistry, University of Pennsylvania, Philadelphia PA
E-mail: [email protected]
We will present the reactivity of a transient titanium alkylidyne (PNP)Ti≡C tBu (PNP = N[2-P(CHMe2)24-methylphenyl]2–), specifically how this species engages in intermolecular C-H activation and
functionalization reactions. Such species can dehydrogenate methane, and C2-C8 alkanes selectively at
the terminal position (in the case of linear alkane C4-C8) to form the olefin product. The mechanism to
this transformation as well as other new reactions such as the dehydrogenation of cyclohexane and
trapping reactions will be presented and discussed. A new catalytic cycle for dehydrogenation of alkanes
will be also discussed as well as the formation of new Ti-C mulitiply-bonded scaffolds such as
phosphino-alkylidenes and alkylidynes and phosphonio-alkylidynes.
O1
1,2,4,6-Thiatriazinyl Radicals and Dimers: Structural and Electronic
Tuning through Heteroaromatic Substituent Modification
Nathan J. Yutronkie, Alicea A. Leitch, Jacob A. Klein, Ilia Korobkov, and Jaclyn L. Brusso*
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa,
ON, Canada
[email protected]; jbrusso@uottawa,ca
For some time, thiazyl-based neutral radicals have been
recognized as attractive candidates for molecular conductors and
magnets, in addition to implementation as spin-bearing ligands or
liquid crystalline radicals. The 1,2,4,6-thiatriazinyl (TTA) radical
is an ideal system in regards to the aforementioned applications as
variation in the R substituent can be used to alter the molecular
and solid state properties. To this end, a series of TTA radicals
have been prepared and investigated with substituted heteroaromatic susbstituents (e.g. thienyl,
pyridyl, pyrimidyl). The 3,5-bis(2-pyridyl)-1,2,4,6-thiatriazinyl (Py2TTA) and 3,5-bis(2pyrimidyl)-1,2,4,6-thiatriazinyl (Pm2TTA) radicals can been viewed as attractive candidates
towards spin-bearing ligands with binding motifs sturcturally similar to terpyridine. Additionally,
the 3,5-bis-(2-thienyl)-1,2,4,6-thiatriazinyl radical (Th2TTA) has been targeted as building
blocks in multifuctional materials as facile functionalization on the thienyl substutuents can give
rise to the potential of discotic liquid crystalline materials. This presentation will focus on the
development of these radicals in regards to their synthesis, characterization, and crystal structures.
Notes:
O2
‘All Three-in-One’: Ferromagnetic Interactions, Single-Molecule
Magnetism and Magnetocaloric Properties in a New Family of [Cu4Ln]
Clusters
Paul Richardson,1 Dimitris I. Alexandropoulos,1 Luís Cunha-Silva,3 Giulia Lorusso,4 Marco
Evangelist,4 Jinkui Tangi,2 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; State Key Laboratory of Rare
Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
3
Changchun, P. R. China; REQUIMTE / LAQV & Department of Chemistry and Biochemistry, Faculty of
4
Sciences, University of Porto, Porto, Portugal; Instituto de Ciencia de Materiales de Aragón (ICMA) and
Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, Zaragoza, Spain
[email protected]; [email protected]
Modern coordination chemistry, as a field of scientific research, has expanded greatly over the
past decades, finding interests in not only isolating aesthetically pleasing structures, but also
probing the magnetic properties of these compounds, such as single-molecule magnetism (SMM)
or the magnetocaloric effect (MCE). These two phenomena share common characteristics; both
are enhanced by a high-spin ground state, which mainly arises
from ferromagnetic interactions between the metal ions present.
The desire for high-spin molecules, which is aided by a large
number of unpaired electrons in the metal ion(s), lead to the
employment of lanthanide (Ln) ions, either in homometallic 4for heterometallic 3d/4f-chemistry. To form such high-spin
molecules, the use of different ligands must be investigated; both
bridging and chelating ligands are necessary to increase the
nuclearity and thermodynamic stability of the compound and
simultaneously prevent the extensive polymerization of the
metal ions. Through the use of the bridging and chelating Figure. Structure of [Cu Gd(nd) ]54
8
ligand naphthalene-2,3-diol (ndH2), a new [Cu4Ln] family of
clusters was isolated and characterized (Figure). This family was studied in detail with respect to
their magnetic properties, searching for SMM behaviour in both the Tb III and DyIII analogues, as
well as MCE in the GdIII analogue.1
1.
P. Richardson, D. I. Alexandropoulos, L. Cunha-Silva, G. Lorusso, M. Evangelisti, J. Tang, Th. C. Stamatatos,
Inorg. Chem. Front. 2015, 2, 945.
Notes:
O3
Study of a Novel Hepta-coordinated FeIII Bimetalic Complex with an
Unusual 1,2,4,5-Tetrazine-Ring Opening
Maykon A. Lemes,a Amélie Pialat,a Stephan N. Steinmann,b Ilia Korobkov,a Carine Michel,b
and Muralee Murugesua,*
a
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada;
Laboratoire de Chimie UMR5182, Université de Lyon, CNRS, Ecole Normale Supérieure de Lyon, Lyon
cedex 07, France
b
Reaction of Fe(NO3)3 with 3,6-di(pyrimidin-2-yl)-1,2,4,5-tetrazine (BPymTz) in acetonitrile
gives a hepta-coordinated FeIII complex (1) with the bridging unit 1,2-diiminohydrazido (1,2dih2- : —HN—C(R)=N—N=C(R)—NH—) generated in-situ from the tetrazine ring-opening of
BPymTz. DFT calculations, X-ray diffraction studies and SQUID magnetometry measurements,
have been performed on 1. The crystallography measurement confirms the ring-opening and the
substituent’s contribution to the rare pentagonal bipyramidal coordination geometry of the metal
ions. Magnetic susceptibility measurements performed on 1 reveal an S = 0 ground state, arising
from a weak antiferromagnetic interaction between the two FeIII centres (J = -3.025 cm-1).
Notes:
O4
A Mononuclear Supramolecular Capsule with Single Molecule Magnet
Behaviour
Majeda Al Hareri, Emma Gavey, and Melanie Pilkington*
Department of Chemistry, Brock University, St. Catharines, ON, Canada
Many lanthanide ions display great potential in the field of molecular
magnetism due to their high intrinsic anisotropies1, which can be
enhanced by an appropriate coordination environment. However, many
of the ligand systems employed to date require multi-step syntheses
and result in complexes which are unstable to air or moisture.1,2 Our
approach has been to make use of the inherently oxophilic nature of
lanthanide ions and employ oxygen-rich ligands, such as the tuneable
crown ethers. Our group has recently reported the synthesis of a novel
family of half-sandwich and sandwich-like complexes that exhibit
single molecule magnet (SMM) behaviour.3 A new addition to this family, a mononuclear DyIII
capsule (1) comprising of three H-bonded benzo-15-crown-5 ligands, also exhibits the slow
relaxation of magnetization consistent with SMM properties. This family collectively represents
the first example of the exploitation of crown ethers as ligands for the formation of mononuclear
lanthanide SMMs.
1
D. N. Woodruff, R.E.P. Winpenny, R.A. Layfield, Chemical Reviews, 2013, 113, 7, 5110-5148.; 2 F. Chibotaru, M.
Murugesu et al., Journal of the American Chemical Society, 2013, 135, 3502-3510.; 3 M. Pilkington et al., J. Mater.
Chem. C, 2015, 3, 7738.
Notes:
O5
New Ruthenium (II) Complex with Pyrazole Containing Ligand and Its
Catalytic Activity in Transfer Hydrogenation
Iryna D. Alshakova and Georgii I. Nikonov*
Ruthenium occupies a prominent position in catalytic hydrogenation and transfer hydrogenation
(TH) of unsaturated substrates. Several families of bifunctional Ru-based catalysts have been
developed. Recently, heterocycle-based ligands have received significant attention, and in
particular pyrazole-supported Ru complexes were found to be effective in the catalytic TH.[1]
Given these literature precedents and our previous research on phosphine supported catalytic TH
of challenging substrates, we designed of a new bifunctional pyrazole-phosphine ligand (N,P).
Screening of potential Ru catalysts resulted in the preparation of complex 1 which happened to
be a highly active catalyst for the TH of nitriles, olefins, and heteroaromatics.
1
[1] a) S. F. L. T. Ghoochany, Y. Sun, and W.R. Thiel, Eur. J Inorg. Chem. 2011, 3431-3437; b) P. W. W. Du, Q.
Wang, and Z. Yu, Organometallics 2013, 32, 3083-3090.
Notes:
O6
Electronic Structure and Bonding in Iron(II) and Iron(I) Complexes
Bearing Bisphosphine Ligands of Relevance to Iron-Catalyzed C-C
Cross-Coupling
Jared L. Kneebone, Valerie E. Fleischauer, Stephanie L. Daifuku, Ari A. Shaps, Joseph M.
Bailey, Theresa E. Iannuzzi, and Michael L. Neidig*
Department of Chemistry, University of Rochester, Rochester, NY, USA
Chelating phosphines are effective additives and supporting ligands for a wide array of ironcatalyzed cross-coupling reactions. While recent studies have begun to unravel the nature of
reactive iron intermediates in several of these reactions,1,2 insight into the origin of differential
effectiveness of bisphosphine ligands in catalysis as a function of their backbone and peripheral
steric structures remains elusive. Herein, we report a spectroscopic and computational
investigation of well-defined iron(II) FeCl2(PP) complexes (PP = SciOPP, dpbz, tBudppe,
Xantphos) as well as 5-coordinate (5C) iron(I)
variants FeCl(dpbz)2 and FeCl(dppe)2 to
systematically discern the relative effects of
bisphosphine backbone character and steric
substitution on overall electronic structure and
bonding within iron complexes in oxidation
states implicated to be relevant in catalysis.
Magnetic circular dichroism (MCD) and
density functional theory (DFT) studies
demonstrate that common ortho-phenylene
and saturated ethyl backbone motifs result in similar ligand field magnitudes and ironbisphosphine bonding character within both the iron(II) and iron(I) series studied. Coordination
of Xantphos to FeCl2 results in a significantly reduced ligand field relative to its iron(II) partners,
where large bite angle and reduced iron-phosphorus Mayer bond orders (MBOs) could play a
role in fostering the unique ability of Xantphos to be an effective additive in Kumada and
Suzuki-Miyaura alkyl-alkyl cross-couplings. Lastly, it has been found that the peripheral steric
bulk of the SciOPP ligand does little to perturb the electronic structure of FeCl 2(SciOPP) relative
to the analogous FeCl2(dpbz) complex. This observation suggests that the origin of differential
catalytic effectiveness of SciOPP and dpbz ligands in Kumada and Suzuki-Miyaura aryl-alkyl
cross-coupling reactions likely originates from ligand steric properties dictating alternative
reduction pathways rather than from inherent differences in iron electronic structure.
(1) Daifuku, S. L.; Al-Afyouni, M. H.; Snyder, B. E. R.; Kneebone, J. L.; Neidig, M. L. J. Am. Chem. Soc. 2014,
136, 9132. (2) Daifuku, S. L.; Kneebone, J. L.; Snyder, B. E. R.; Neidig, M. L. J. Am. Chem. Soc. 2015, 137,
11432.
Notes:
O7
Aqueous Biphasic Iron-Catalyzed Asymmetric Transfer
Hydrogenation of Ketones
Karl Z. Demmans, Oliver W. K. Ko,* and Robert H. Morris*
Department of Chemistry, University of Toronto, Toronto, ON, Canada
[email protected]; [email protected]; [email protected]
For the first time, an iron (II) catalyst is used in the biphasic asymmetric transfer hydrogenation
(ATH) of ketones to enantioenriched alcohols employing water and potassium formate as the
proton and hydride source. The precatalyst [FeCl(CO)(P-NH-N-P)][BF4] (P-NH-N-P = (S,S)PPh2CH2CH2NHCHPhCHPhNCHCH2PPh2) in the organic phase with the substrate is activated
by base to produce a system that rivals the best ruthenium biphasic ATH catalysts in activity but
not enantioselectivity. Biorenewable 2-methyltetrahydrofuran was added as a cosolvent to
greatly enhance the catalyst’s activity. The enantioselectivity of the reduction ranged from 3 to
88% depending on the substitution pattern of the arylketone employed. NMR studies verify the
formation of an iron hydride [FeH(CO)(PPh2CH2CH2NHCHPhCHPhNCHCHPPh2] intermediate
as was observed in our 2-propanol-based ATH studies.
Notes:
O8
Catalyst Choice in Cross-Metathesis of Electron-Deficient Olefins:
Phosphine-Induced Catalyst Decomposition
Gwendolyn A. Bailey and Deryn E. Fogg*
Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada
In the past two years, olefin metathesis has seen its
long-awaited implementation in pharmaceutical and
specialty-chemicals manufacturing.1,2 Fundamental
questions relating to catalyst deactivation pathways
hence take on intensified importance. We recently
described the incompatibility of the dominant Grubbs
catalyst GII (Chart 1) with acrylates. The PCy3
ligand used to stabilize the precatalyst reacts with these electron-deficient olefins to generate
strongly basic enolate A, which then triggers catalyst decomposition by abstracting a proton from
the metallacyclobutane intermediate.3 The scope of this behaviour is of keen interest from the
emerging perspective of metathesis of directly-functionalized olefins. Here we explore its
dependence on the electronic nature of the olefin substituent, and on the basicity of the
phosphine ligand.
[1] (a) Nickel, A.; Pederson, P. L. in Olefin Metathesis – Theory and Practice (Ed.: K. Grela), Wiley, Hoboken,
2014, pp. 335–348. (b) Fandrick, K. R.; Savoie, J.; Yee, N; Song, J. J.; Senanayake, C. H. in Olefin Metathesis –
Theory and Practice (Ed.: K. Grela), Wiley, Hoboken, 2014, pp. 349–366.
[2] Higman, C. S.; Lummiss, J. A. M.; Fogg, D. E. Angew. Chem. Int. Ed. 2016, accepted.
[3] Bailey, G. A.; Fogg, D. E. J. Am. Chem. Soc. 2015, 137, 7318–7321.
Notes:
O9
Synthesis and Characterization of Side-Chain Boron Difluoride
Formazanate Polymers
Samantha Novoa, Joseph A. Paquette, Stephanie M. Barbon, Ryan R. Maar, and Joe B. Gilroy*
Department of Chemistry, Western University, London, ON, Canada
Boron difluoride (BF2) complexes of formazanate ligands
(e.g., 1) are a class of molecular materials that offer
structurally tunable spectroscopic properties, moderate to
high fluorescence quantum yields and redox activity.1 Due
to their promising properties, we set out to incorporate
triaryl formazanate BF2 complex 1 into polymers 2
through ring-opening metathesis polymerization (ROMP)
of a pendant norbornene group using Grubbs' 3rd
generation catalyst (GIII).2 Mechanistic studies revealed
the controlled nature of this polymerization. Moreover, the unique properties of the BF2 complex
were retained upon polymerization. The polymers are strongly absorbing in the visible region,
are fluorescent, exhibit large Stoke's shifts, and can be reversibly reduced to borataverdazylbased poly(radical anions) electrochemically. Recent progress in this area will be presented.
1. S. M. Barbon, P. A. Reinkeluers, J. T. Price, V. N. Staroverov and J. B. Gilroy, Chem. Eur. J., 2014, 20,
1134011344.
2. S. Novoa, J. A. Paquette, S. M. Barbon, R. R. Maar, J.B. Gilroy, 2015, Submitted.
Notes :
O10
Alkyl-functionalization of 3,5-bis-(2-pyridyl)-1,2,4,6-thiatriazine
Complexes
Elizabeth Kleisath, Nathan Yutronkie, Ilia Korobkov, Bulat Gabidullin, and Jaclyn Brusso*
Department of Chemistry, University of Ottawa, Ottawa, ON, Canada
A novel synthesis of alkyl-functionalized 3,5-bis(2-pyridyl)-4-hydro-1,2,4,6-thiatriazine
(Py2TTAH) complexes through post thiatriazine (TTA) ring formation will be presented. This
marks the first reported example of S-alkylation in TTA complexes starting from a stable
synthetic precursor. Either discrete cations or coordination polymer structures are obtained,
depending on the electrophilicity of the alkylating agent used. In addition, the relative
susceptibility of the Py2TTAH heteroatoms towards alkylation was determined; initial alkylation
occurred at the sulfur of the TTA ring, and then additionally on the nitrogen atoms of the
pyridine substituents. Single crystal X-ray analysis highlights the differences in chemical
environment and crystallographic packing between the discrete molecules in comparison to the
1D coordination polymer. The versatile heteroatom-alkylation synthesis for TTAs will be
presented, along with characterization studies of the resulting compounds.
Notes:
O11
Towards Highly Conjugated and Functional Materials: the Quest for
Polyazaborinines
Soren Mellerup and Suning Wang*
Department of Chemistry, Queen’s University, Kingston, ON, Canada
Recently, our research group observed that BN-heterocycles (B; Figure 1) display unique
reactivity when exposed to different stimuli such as heat or light, ultimately generating either
pyrido[1,2-a]isoindole (A) or BN-phenanthrenes (C) respectively.1 Due to the simplicity and
selectivity of each transformation, we set out to design new precursors consisting of multiple
BN-heterocyclic components such that the application of either heat or light would induce the
formation of highly -conjugated materials containing several pyrido[1,2-a]isoindole or BNphenanthrene functionalities. This presentation will focus on the synthesis of these interesting
molecules, their photo/thermal reactivities, and evaluation of the highly conjugated products.
Figure 1. The varying reactivity of BN-heterocyles B.
1) Yang, D.T.; Mellerup, S.K.; Wang, X.; Lu, J.S.; Wang, S. Angew. Chem. Int. Ed. 2015, Accepted.
Notes:
O12
Towards Carrier-Mediated Water Splitting – Catalytic Dehydrogenation
of Formaldehyde
Nicholas Alderman, Camilo Viasus, Jacob Sommers, Virginie Peneau, Laura Hull, Salimah Alshehri, and
Sandro Gambarotta*
A major problem with current photochemical water splitting systems such as TiO2 is the
inhibitive cost of gas (O2/H2) separation, which can add hundreds of million dollars to plant
designs. Therefore a system which can release carbon and hydrogen in two different
environments would negate the need for expensive gas separation. We propose a catalytic cycle
based upon the oxidation and reduction of a carbon carrier, expelling hydrogen in one step and
re-hydrogenation (using water and releasing oxygen) in another step. We have been investigating
the use of the formaldehyde-formate couple, and show promising preliminary results in an
overall water splitting cycle using this technique.
Notes:
O13
Catalytic Hydrogenation of CO2 to Formamide using Non-precious
Metal Catalysts
Mohammad A. Affan and Philip G. Jessop*
Catalytic hydrogenation of CO2 is an efficient and selective way to form value added fine
chemicals such as formic acid derivatives, but most of the highly active catalysts have required
precious metals. Eighteen non-precious metal precursors have been screened with six types of
phosphine/hemilabile ligands for the catalytic hydrogenation of CO2 with morpholine to
formamide. Twelve non-precious metal precursors have also been screened with two
diphosphine ligands for the catalytic hydrogenation of CO2 with 2-ethylhexylamine to
formamide. The most active catalysts for the hydrogenation of CO2 for the formylation of
morpholine or 2-ethylhexylamine are [MX2(dmpe)2] (M = Fe(II) and Ni(II); X = Cl-, CH3CO2-;
acac-; dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. Morpholine and 2-ethylhexylamine
are formylated at 100 oC and 135 oC, respectively, at a total pressure of 100 bar. Morpholine was
formylated with a TON up to 18,000, which is approaching the range of TON values reported for
noble metal-phosphine complexes. 2-Ethylhexylformamide was obtained with a TON up to
1,600. With the appropriate selection of catalyst and reaction conditions, >90-98% conversion of
amine was achieved to form a formamide.
Notes:
O14
Ruthenium and Iridium Complexes of Poly-pyridine Ligands as
Homogeneous Catalysts for the Hydrodeoxygenation of Biomassderived Substrates to Value-added Chemicals
Elnaz Latifi, Ryan J. Sullivan, Thomas A. Minard, Christopher T. Oswin, and Marcel Schlaf*
Department of Chemistry, University of Guelph, Guelph, ON, Canada
The series of the water-soluble tri/tetradentate amino-poly-pyridine ligand based homogeneous
Ruthenium/Iridium catalysts (1-5) was evaluated for the conversion of biomass derived 2,5hexanedione and 2,5-dimethylfuran to the hydrodeoxygenated value-added products 2,5hexanediol, 2,5-dimethyltetrahydrofuran and hexane in aqueous acidic medium at high
temperatures (150−225 °C) under hydrogen gas (5.5 MPa). The systems are active but limited by
thermal decomposition. Catalyst (1) decomposes at T ≥ 225 °C to the inactive bis-chelate
complex [(4′-Ph-terpy)2Ru]2+ and an inactive metallic ruthenium coating. 2 decomposes at T >
175 °C acting as a heterogeneous Ir0 catalyst. 3 decomposes at T ≥ 175 °C by formation of
marginally active Ru0. 4 also shows good activity for the conversion of 2,5-hexanedione to 2,5hexanediol and 2,5-dimethyltetrahydrofuran at 175 and 200 °C with decomposition observed
only at T ≥ 225 °C. 5 is capable of converting 5-hydroxy-methylfurfural-acetone aldol adducts to
the highly valuable 2,5,8-nonatriol in moderate yields, but deactivation via formation of the bischelate was again observed at T ≥ 200 °C.
Notes:
O15
A Fluorescent Radical-Functionalized Poly-Aromatic Hydrocarbon
Polymer Composite
Mitchell Nascimento, Yassine Beldjoudi, Igor Osorio-Roman, and Jeremy M. Rawson*
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada
Radicals have recently been proposed as excellent candidates for light-emitting devices such as
OLEDs due to their theoretical 100% efficient doublet excitation/relaxation process1. Here we
describe a phenanthrene-functionalised dithiadiazolyl radical (1). The radical is a diamagnetic
dimer in the solid state but dissociates to form monomers in solution.
Spectroscopic studies reveal excitation at 254 nm affords a bright blue
emission at 410 nm. TD-DFT studies indicate that the initial absorption
giving rise to the fluorescence is not radical based and the nonparticipation of the radical electron in the fluorescence process is
evidenced by the observation that the salt [1][GaCl4] exhibits a similar
broad emission at 410 nm. Incorporation of 1 into PMMA and PS
polymer matrices afford smooth homogeneous blue emissive polymer
films whose lifetimes are 10 to 100 times greater than 1 in solution.
1. Q. Peng, A. Obolda, M. Zhang and F. Li, Angew. Chem. Int. Ed., 2015, 54, 7091.
Notes:
O16
Multichromic Supramolecular Dye Architectures for Advanced LightHarvesting Applications
Muhammad Yousaf and Bryan D. Koivisto*
Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada
Shape-persistent phenylacetylene macrocycles have been explored in a number of optoelectronic
and light-harvesting applications, including two-photon absorption. Likewise, BODIPY (4,4difluoro-4-bora-3a,4a-diaza-s-indacenes) dyes have also been extensively used in material
applications, owing to their tunable, intense absorption and sharp emission peaks exhibiting high
quantum yields. Employing the BODIPY molecule orthogonal to the phenylacetylenemacrocycle results in energy transfer from macrocycle to the BODIPY core. The novel dye
design could potentially be used in the dye-sensitized solar cells (DSSCs). The DSSC is a nextgeneration photovoltaic device that incorporates a dye molecule as a light-absorber. The dyes for
the DSSC are generally comprised of a redox-active donor/chromophore (D) that is coupled
through a conjugated linker (π) to an acceptor (A) capable of anchoring to TiO2 (i.e. D-π-A
motif). The BODIPY-macrocycle dye motif can be used as a π-spacer in the DSSC dye (as
shown in Fig.) and could permit two-photon absorption resulting in panchromatic absorption.
Notes:
O17
The Formation of Gold Thiophene Nanoreactor By Mediating MetalPolymer Interaction
Vishva Shah,1 Cecile Malardier-Jugroot,1,* and Manish Jugroot2
1
2
Department of Chemistry and Chemical Engineering; Department of Mechanical and Aerospace
Engineering, Royal Military College of Canada, Kingston, ON, Canada
Gold nanoparticles have many applications in a variety of fields ranging from clinical chemistry
to targeted drug delivery. The size and the shape of the nanoparticles have proven to be
important factors in determining the physical and electronic properties of the nanoparticles, it is
therefore important to use a template for the synthesis of highly ordered gold
nanoparticles. Poly(styrene-alt-maleic acid), SMA, is an amphiphilic alternating co-polymer
which self assembles in water into highly organized nanostructures and is a good candidate for
use as a template. Indeed, this template has been used successfully for an environmentally
friendly synthesis of organic polymers (polypyrrole) as well as metal nanoparticles(gold and
platinum). Pyrrole was found to spontaneously polymerize within the confined hydrophobic
cavity of SMA whereas gold was found to form an atomically-thin gold monolayer on the outer
hydrophilic surface of SMA. In this study, we combined both of these results to control the
interaction between SMA and gold in three ways including sonication, altering the nature of the
polymer and by using thiophene, a structurally similar molecule to pyrrole, to exploit the wellknown gold-sulphur bond to draw the gold(I) chloride precursor into the confined regions of
SMA. Since thiophene makes a strong bond with gold, we also studied the effect of this
interaction on the interaction between gold and SMA, which could make the hydrophobicity or
hydrophillicity of the metal salt irrelevant. Moreover, it was previously observed
that the confined cavities of SMA also forced the direct reduction of hydrophobic metal salts into
platinum nanoclusters. The role and the effect of the interaction between the hydrophilic or
hydrophobic cavities of the template and the metal salt on the shape and size of the gold
nanoparticles will be emphasized. The ability to mediate the metal-polymer interaction by a
coupling agent opens up many more possibilities for applications in medicine, industry, and
academia.
Notes:
O18
Electrochemical Characterizations of Ultra-stable Self-assembled
Monolayers of N-heterocyclic Carbenes on Gold
Zhe She,1,2 Mina R. Narouz,3 Christene A. Smith,3 Cathleen M. Crudden,3,4 J. Hugh Horton,3 and
Heinz-Bernhard Kraatz1,5,*
1
Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, ON,
2
Canada; Department of Chemistry and Chemical Engineering, Royal Military College of Canada,
3
4
Kingston, ON, Canada; Department of Chemistry, Queen's University, Kingston, ON, Canada; Institute
5
of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, Japan; Department
of Chemistry, University of Toronto, Toronto, ON, Canada
A self-assembled monolayer (SAMs) is a layer of organic molecules assembled at surfaces often
stabilized by high binding affinities between the molecules and the surface substrate and by van
der Waals interactions between adjacent molecules. Film formed by the interaction of Scontaining molecules and Au surfaces giving rise to strong Au-S bonding has dominated this
area of research since the first reports of Au-thiolate films by Nuzzo and Whitesides et al. (1).
Recently, N-heterocyclic carbenes based SAMs were reported to be more stable than traditional
Au-S SAMs (2). Here, we report the electrochemically characterization of these films, and
provide information of their stability, molecular density and electron transfer properties of
carbene films.
(1) Bain, C. D.; Troughton, E. B.; Tao, Y. T.; Evall, J.; Whitesides, G. M.; Nuzzo, R. G. J. Am. Chem. Soc. 1989,
111, 321.
(2) Crudden, C. M.; Horton, J. H.; Ebralidze, I. I.; Zenkina, O. V.; McLean, A. B.; Drevniok, B.; She, Z.; Kraatz, H.B.; Mosey, N. J.; Seki, T.; Keske, E. C.; Leake, J. D.; Rousina-Webb, A.; Wu, G. Nature Chemistry 2014, 6, 409.
Notes:
O19
Synthesis and Coordination of Amidines and Phosphaamidines Metal
Complexes
Ramjee Kandel, Keith Huynh, Lauren Dalgliesh, Ruiyao Wang, and Philip G. Jessop*
Transition metal complexes incorporating amidines and phosphaamidines ligands, have
received less attention and coordination chemistry is less known. They could interesting for their
coordination chemistry and possibly of catalysis.
Amidines are nitrogen containing bases where the unsaturated nitrogen is more active
towards coordination and can be easily protonated. Research in our laboratory has exploited the
basicity of amidines as promoters of CO2 fixation to other products, while phosphaamidines are
hybrid ligands containing a basic hard donor nitrogen atom and a soft donor phosphorus atom.
The design of acyclic phosphaamidine is attractive as the tunable Nimine should retain its basicity
while the P should preferentially coordinate to the most transition metals.
In this light, we have prepared a series of tunable acyclic amidines and phosphaamidines
and tested their coordinating abilities with Cu(I) and other transition metal ions. Amidines
coordinated through only Nimine leaving Namine free while phosphaamidines coordinate through
phosphorus and Nimine depending upon the electronic and steric properties of the
phosphaamidines.
Notes:
O20
Manganese(II) Dialkyl and Manganese(I) and (III) Hydride Complexes
Jeffrey S. Price, Preeti Chadha, and David J. H. Emslie*
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada
With a view towards the development of new organometallic precursors and reactivities for
manganese metal atomic layer deposition (ALD), the solid state structures and properties of
[{Mn(μ-R)2}∞] (1; R = CH2SiMe3), [{Mn(R')(μ-R')2}2{Mn(μ-R')2Mn}] (2; R' = CH2CMe3),
[Mn(R)2(dmpe)] (3; dmpe = 1,2-bis(dimethylphoshino)ethane), [{Mn(R')2(μ-dmpe)}2] (4),
[{Mn(R)(μ-R)}2(μ-dmpe)] (5), [{Mn(R')(μ-R')}2(μ-dmpe)] (6), [{Mn(R)(μ-R)}2(μ-dmpm)] (7;
dmpm = bis(dimethylphoshino)methane), and [{Mn(R')(μ-R')}2(μ-dmpm)] (8) are reported.
Syntheses for 1-4 have previously been published, but the solid state structures and most
properties of 2-4 had not been described. Compounds 5 and 6, with a 1:2 dmpe:Mn ratio, were
prepared by reaction of 3 and 4 with base-free 1 and 2, respectively. Compounds 7 and 8 were
accessed by reaction of 1 and 2 with 0.5 or more equivalents of dmpm per manganese. An X-ray
structure of 2 revealed a tetrametallic structure with two terminal and six bridging alkyl groups.
The solid state structures of bisphosphine-coordinated 3-8 revealed three distinct structure types:
(a) monometallic [LMnX2], (b) dimetallic [X2Mn(µ-L)2MnX2], and (c) dimetallic [{XMn(µX)}2(µ-L)] (X = R or R'; L = dmpe or dmpm). Reactions of 1-8 with H2 (25-120 °C) afforded
manganese metal. By contrast, reaction of 1-8 with ZnEt2 (25 °C) afforded a ~ 1:1 Mn:Zn alloy,
accompanied in the case of dmpe-containing 3-6 by the formation of [Mn(dmpe)2(ethylene)(H)]
(9). The solid state structure of 9 is reported, along with oxidative addition reactivity leading to
new manganese(III) hydride complexes.
Notes:
O21
Nitrene Transfer from Organic Azides Mediated by Metal Complexes
of Bulky o-Phenylenediamide Ligand
Pavel Zatsepin, Trevor Janes, and Datong Song*
The direct amination of C-H bonds is an area of great interest to synthetic chemists1 as a means
to access the wide range of useful molecules with nitrogen-containing functionalities2. One way
to achieve this transformation is to insert nitrenes into C–H bonds,3 where metal complexes have
been used to stabilize nitrenes and improve the selectivity.4,5 In this presentation the reactivity of
bulky phenylenediamide (pda) complexes towards organic azides in nitrene formation and
transfer reactions will be discussed . One example is shown below.
1.
2.
3.
4.
5.
Sharma, A.; Hartwig. J. F. Nature., 2015, 517, 600-604.
Hili, R.; Yudin, A. K., Nat. Chem. Biol., 2006, 2, 284-287.
Egger, J.; Carreira, E. M., Nat. Prod. Rep., 31, 451-453.
Hennessy, E. T.; Betley, T. A. Science., 2013, 340, 591-595.
Ramirez, T. A.; Zhao, B.; Shi, Y., Chem. Soc. Rev., 2012, 41, 931-942
Notes:
O22
Solvent Stabilized Dinitrogen Trioxide as a Laboratory Reagent
Kristopher Rosadiuk and D. S. Bohle*
Department of Chemistry, McGill University, Montreal, QC, Canada
Dinitrogen trioxide (N2O3) is normally stable only under extremely cold temperatures, and quickly
dissociates into NO and NO2 upon warming. A little known fact is that N2O3 may be stabilized by
dissolving it in organic solvents. This presentation describes the handling of these solutions and explores
some of the novel ways that it has been used in our lab, such as the production of tertiary amine adducts
and polymercury salts.
Notes:
O23
Evaluation of Anisole-Substituted Boron Difluoride Formazanate
Complexes for Fluorescence Cell Imaging
Ryan R. Maar, Stephanie M. Barbon, Neha Sharma, Hilary Groom, Leonard G. Luyt, and Joe
B. Gilroy*
Fluorescent materials have been known for nearly a century, and are
attractive targets for scientists in research fields such as organic electronics,
chemical sensing, and cell imaging. Much of the research in the field of
fluorescent materials has been devoted to four-coordinate boron
compounds with chelating, π-conjugated ligands.1 Recent advances by the
Gilroy group have focused on the synthesis of boron difluoride
formazanate complexes (e.g., 1) which were shown to exhibit tunable
spectroscopic and redox properties.2 This presentation will describe a
systematic study designed to probe the effect of ortho-, meta-, and parasubstitution patterns of anisole rings bound to a boron difluoride
formazanate scaffold. Based on its straightforward, high-yielding synthesis
and impressive fluorescence quantum yield, 1c was chosen for fluorescence
cell-imaging studies. The structural features, spectroscopic characteristics
and electrochemical properties of 1a−c, and the cell-imaging studies of 1c will be discussed in
detail during this presentation.
(1) Ulrich, G.; Ziessel, R.; Harriman, A. Angew. Chem. Int. Ed. 2008, 47, 1184−1201. (2) Maar, R. R.; Barbon, S.
M.; Sharma, N.; Groom, H.; Luyt, L. G.; Gilroy, J. B. Chem. Eur. J. 2015, DOI: 10.1002/chem.201502821.
Notes:
O24
Pyrido[2,1-α]-isoindole as a Novel Ligand in Main Group and
Transition Metal Chemistry
Sean M. McDonald and Suning Wang*
Pyrido[2,1-α]-isoindoles have been synthetically accessible since the 1960s.1,2 However, very
little investigation has been made into their reactive capabilities. The majority of work has gone
into studying cycloadditions with alkynes to produce unique and polarized system.3,4 Due to its
electronic structure, pyrido[2,1- α]-isoindole has nucleophilic character at the 6-position, leading
to great potential for use as a novel ligand in main group and transition metal chemistry. The
Wang group has already showcased the adduct formation with HB(C6F5)2 as an intermediate step
towards 1,1-hydroboration.5 This
work will detail the coordination
chemistry and novel reactivity of
pyrido[2,1-α]-isoindole with main
group elements and transition
metals.
1. Fozard A., Bradsher C. K.; Tetrahedron Lett., 1966, 7, 3341. 2. Fozard A., Bradsher C. K.; J. Org. Chem., 1967,
32, 2966. 3. Kajigaeshi S., Mori S., Fujisaki S., Kanemasa S.; Bull. Chem. Soc. Jpn., 1985, 58, 3547. 4. Mitsumori
T., Bendikov M., Dautel O., Wudl F., Shioya T., Sato H., Sato Y.; JACS, 2004, 51, 16793. 5. Yang D.-T., Mellerup
S. K., Wang X., Lu J.-S., Wang S.; Angew.Chem.Int.Ed., 2015, 54, 5498.
Notes:
O25
Bis-Carbene-Stabilized Phosphorus Cations
Justin F. Binder, Ala’aeddeen Swidan, Martin Tang, Jennifer H. Nguyen, and Charles L. B.
Macdonald *
Phosphamethine cyanine dyes are landmark molecules for main group chemistry in that they
provided the first concrete evidence of 3p-2p π-bonding.1 In spite of this historical relevance,
chemistry involving these low-valent phosphorus compounds remains underexplored. Our group
discovered that the reaction between a triphosphenium salt and carbenes is a safe, convenient
route to such species.2 Investigations into their syntheses, properties and reactivity are presented.
1 P. Jutzi, Angew. Chem. Int. Ed., 1975, 14, 232–245.
2 B. D. Ellis, C. A. Dyker, A. Decken and C. L. B. Macdonald, Chem. Commun., 2005, 1965–1967.
Notes:
O26
Engineered Designer Monomers: The Path to Light and Moisture
Stable Polystannanes
Jeffrey Pau and Daniel Foucher*
Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada
This work continues an investigation into the utility of covalently attached light absorbing
chromophores to protect the light sensitive Sn-Sn backbone of polystannanes. Here the UV
absorbing azobenzene “antenna” is incorporated into a polymerizable tin dihydride monomer
that may lead to interesting homo- and copolystannane materials. Additionally, the flexible
nature of the attached UV chromophore is such
that it can adopt 5-coordinate geometry at Sn to
further protect the sensitive Sn-Sn polymer
bonds from nucleophilic attack. In this work, we
present syntheses of azostannyl compound 5
achieved through a Williamson ether synthesis.
Compound 5 is then sequentially chlorinated to
the mono- 6 and dichlorostannane 7. Compound
8 was then obtained by hydrogenation of 7 with
LiAlH4. The azo-stannyl monomer 8 was then
reacted with a suitable transition metal catalyst
that promoted dehydropolymerization to the
polystannane 9. All structures were confirmed by
NMR (1H, 13C, 119Sn, HSQC) and in the case of 5 and 6, an X-ray crystal structure analysis. The
UV behaviour of the azo-stannyl compounds were also probed by UV-Vis spectroscopy.
Investigations show that the cis- (n-p*) and trans- (p-p*) light switching characteristics of
azobenzene are preserved in the stannyl compounds.
Notes:
O27
N-Heterocyclic Carbene Stabilized Ag Nanoparticles
Iraklii I. Ebralidze1 and Heinz-Bernhard Kraatz1,2*
1
Department of Physical and Environmental Sciences, University of Toronto, Scarborough, ON, Canada;
Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON,
Canada
2
Metal nanoparticles (NPs) are a focus of interest because of their unique properties and thus huge
potential in science and engineering. Silver nanoparticles (AgNPs) as well as silver in ionic form,
are known to possess antimicrobial effects. AgNPs are known to interact with heavy metal ions
such as Hg(II), Hg(I), Pb(II), and Cd(II) showing significant growth in size upon their
incorporation and therefore can be used for drinking water purification.1 Moreover, silver NPs
can be synthesized and modified with various chemical functional groups which allow them to
be conjugated with antibodies, ligands, and drugs of interest and thus opening a wide range of
potential applications in biotechnology, magnetic separation, and pre-concentration of target
analytes, targeted drug delivery, and vehicles for gene and drug delivery and more importantly
diagnostic imaging.2 Even though tremendous number of applications, synthetic routes for
AgNPs are limited to the reduction of Ag+ in presence of stabilizing/capping reagents such as (I)
nonionic surfactants (poly(vinyl pyrrolidone, Triton X-100 ), (II) citrate anions, (III) thiols, or
their mixtures. From this list only thiols form strong bonds with AuNPs and allow further
functionalization to achieve desired modern architectures. Crudden et al.3 have recently shown
that thiols anchored to gold surfaces can be substituted by N-heterocyclic carbenes (NHC) due to
formation of much stronger covalent Au-NHC bond. On the other hand, deprotonation of
azolium salts (NHC precursors) using a silver base (or simultaneously a silver salt and a base)
has been the most widely used method in the syntheses of NHC complexes of silver. Taking this
into mind, we developed a route of formation of AgNPs starting from NHC-Ag complexes. This
route results in AgNPs stabilized by covalently bounded carbenes.
1. M.S. Bootharaju, T. Pradeep. Uptake of toxic metal ions from water by naked and monolayer protected silver
nanoparticles: An x-ray photoelectron spectroscopic investigation, J. Phys. Chem. C. 114(18), 2010, 8328–8336
DOI: 10.1021/jp101988h
2. V.V. Mody, R. Siwale, A. Singh, H.R. Mody. Introduction to metallic nanoparticles. J.Pharm. Bioallied Sci. 2(4),
2010, 282-289. DOI: 10.4103/0975-7406.72127.
3. Cathleen M. Crudden et al. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold. Nature
Chem. 6, 2014, 409–414 DOI: 10.1038/nchem.1891
Notes:
O28
Iterative, Protecting Group Free Suzuki-Miyaura Coupling of
Enantioenriched Polyboronates
C. Ziebenhaus,1 Jason P. G. Rygus,1 K. Ghozati,1 P. J. Unsworth,1 S. Voth,1 Y. Maekawa,1 C.
M. Crudden,*,1 and M. Nambo2
1
2
Department of Chemistry, Queen’s University, Kingston, ON, Canada; Nagoya University, Japan
The Suzuki-Miyaura cross-coupling is among the most
widely used reactions in chemical synthesis. In particular, it
has found wide applicability in the construction of biaryl or
polyene scaffolds, and has been proposed as the key reaction
for the modular, automated assembly of such structural
motifs1. Such a process relies on the use of protecting groups
to modulate the activity of various C-B bonds, and thus
requires costly, inefficient protection and deprotection steps
for each bond forming sequence. Herein we describe a
significant advancement in the field of iterative crosscoupling of polyborylated substrates containing aromatic,
primary aliphatic and second aliphatic C-B bonds2 to generate enantioenriched, multiply arylated
structures without the use of boron protecting groups. We demonstrate chemoselective crosscoupling based solely on the intrinsic differences in reactivity imparted by the nature of the C-B
bond.
1
2
Woerly E.M., Roy J. & Burke M.D., Nature Chem. 2014, 6, 484
Imao D., Glasspoole B.W., Laberge V.S. & Crudden C.M. J. Am. Chem. Soc. 2009, 131, 5024
Notes:
O29
Chan-Lam Coupling Using a Copper(II) Complex with a Sulfonated
Diketimine Ligand
Valérie Hardouin Duparc and Frank Schaper*
Département de chimie, Université de Montréal, Montréal, QC, Canada
Chan-Lam coupling is a well-known cross-coupling reaction between an aryl boronic acid and an
alcohol or an amine in presence of copper(II) to form a C-O or C-N bond.1 While
environmentally friendly and economic, several aspects of Chan-Lam couplings can still be
optimized: reaction conditions often need to be adapted for the substrate, stoichiometric amounts
of copper are sometimes required and presence of base is normally necessary.2
We recently synthetized copper complexes based on sulfonated diketimine ligands,3 and studied
their structural features and stability.
The obtained complexes were then tested in Chan-Lam coupling and proved to work under mild
condition and to be applicable to a variety of amine substrates.
1
(a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933. (b) Evans, D.
A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937. (c) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams,
J.; Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941.
2
(a) Ley, S. V.; Thomas, A. W. Angew. Chem. Int. Ed. 2003, 42, 5400 (b) Allen, S. E.; Walvoord,R. R.; PadillaSalinas, R.; Kozlowski, M. C. Chem. Rev. 2013, 113, 6234.
3
Rajendran, N. M.; Reddy, N. D. Polyhedron 2014, 72, 27.
Notes:
O30
Stable Organopalladium(IV) Aryldiazenido Complexes
David Armstrong,1 Marzieh Daryanavard,1 Alan J. Lough,2 and Ulrich W. Fekl*,1
1
2
University of Toronto Mississauga, Mississauga, ON, Canada; University of Toronto, Toronto, ON,
Canada
The usefulness of palladium complexes as
catalysts in organic synthesis, for a range of C-C
and C-X coupling reactions, is well recognized.1
The 2010 Nobel Prize in Chemistry was awarded
to Heck, Negishi, and Suzuki for their work on
palladium catalyzed cross-coupling reactions.2
Mechanistically, the vast majority of catalytic
cycles involve a Pd(0)/Pd(II) redox couple.1,3
While there have been some recent reports of the
involvement of Pd(III) and Pd(IV)4 in some
catalytic cycles, much less is known about the
catalytic potential of Pd(II)/Pd(IV) redox pairs.5 We have demonstrated the synthesis and
characterization of the first palladium(IV) aryldiazenido complexes, formed by the oxidation of
(Tp*)PdMe2 (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) using aryldiazonium salts.
Thermolysis of these compounds leads to substituted biphenyls via C-C coupling. Synthesis and
reactivity will be discussed, as well as implications for palladium catalysis involving high
oxidation states of palladium.
1
Negishi, E. Handbook of Organopalladium Chemistry for Organic Synthesis; John Wiley & Sons: Hoboken, NJ,
2002.
2
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/.
3
(a) van Leeuwen, P. W. N. M. Homogeneous Catalysis: Understanding the Art; Kluwer: Dordrecht, The
Netherlands, 2004.
4
(a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (b) Xu, L.-M.; Li, B.-J.; Yang, Z.; Shi, Z.-J. Chem.
Soc. Rev. 2010, 39, 712. (c) Canty, A. J. Dalton Trans. 2009, 10409.
5
(a) Khusnutdinova, J. R.; Qu, F.; Zhang, Y.; Rath, N. P.; Mirica, L. M. Organometallics 2012, 31, 4627. (b)
Chuang, G. J.; Wang, W.; Lee, E.; Ritter, T. J. Am. Chem. Soc. 2011, 133, 1760.
Notes:
O31
Selective C(sp2)-O Bond Formation from Palladium Complexes by
Using a Green Oxidant
Ava Behnia, Johanna M. Blacquiere*, and Richard J. Puddephatt *
Palladium-catalyzed cross-coupling reactions have revolutionized the ability to form C–
heteroatom bonds as well as C-C bonds. Generation of oxygen containing compounds via C-O
reductive elimination are less common and not well understood. However, C-O bond forming
reductive elimination reactions might be very beneficial for designing more effective and
environmentally benign catalytic reactions where H2O2 is used as oxidant. Recently, Mirica et.
al. have introduced an example of selective C(sp2)-O bond forming reaction from a Pd(IV)
complex with a tridentate N-donor ligand.2 Alternatively, Sanford et. al. observed selective
C(sp3)-O reductive elimination with a Pd complex ligated by a bidentate N-donor ligand.3 These
observations suggest that the nature of the ligand plays a role in controlling selectivity of the
bond forming step. We have targeted a Pd(II) complex with a bidentate N-donor and a
hydrocarbon ligand that can coordinate to the metal center through C(sp2) and C(sp3) centers. We
have treated the Pd(II) complex with different kinds of oxidants to probe the ability to form
stable palladium(IV) complexes or to form new palladium(II) complexes by sequential oxidative
addition/reductive elimination reactions. Use of H2O2 as the oxidant gives a very rare example of
C-O bond formation by oxygen atom insertion into an arylpalladium bond. In our system the PdC(sp2) bond is more reactive than the Pd-C(sp3) bond towards reductive elimination reactions.
(1) Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev., 2002, 102, 1359. (2) Qu, F.;
Khusnutdinova, J. R.; Rath, N. P.; Mirica, L. M. Chem. Commun., 2014, 50, 3036. (3) Camasso, N. N.; PérezTemprano, M. H.; Sanford, M. S. J. Am. Chem. Soc., 2014, 136, 12771.
Notes:
O32
Tuning the Steric and Electronic Properties of Iron-Based Catalysts
Using Modular Phosphine Moieties
Samantha A.M. Smith, Alan J. Lough, and Robert H. Morris*
The asymmetric hydrogenation (AH) of ketones is an efficient method for producing enantioenriched alcohols for the use in industrial processes.i The last decade has proven that the use of
earth-abundant metals as opposed to precious metals is viable for the reduction of polar double
bonds.i-iii Our group has focused on the use of iron in catalysis for both asymmetric transfer
hydrogenation (ATH) and AH.iv Our most recently developed third generation catalystsv,vi are
highly efficient for the reduction of ketones via ATH, but not entirely understood. We became
interested in how the steric and electronic properties of the phosphorus moieties alter catalytic
results and thus we will discuss how the systematic modification of the substituents at one
phosphorus alter the catalyst structures and their activities and selectivities.
1980
1975
ν(CO) (Cm-1)
1970
1965
1960
1955
1950
1945
1940
130
i
140
150
160
Cone Angle (deg)
170
180
R. H. Morris, Acc. Chem. Res. 2015, 48, 1494; ii Ohkuma, Takeshi, et al. JACS., 2006, 128, 8724; iii T. Ikariya, A.
J. Blacker, Acc. Chem. Res., 2007, 40, 1300; iv P. E. Sues, K. Z. Demmans, R. H. Morris, Dalton Trans., 43, 2014,
7650; v W. Zuo, A. J. Lough, Y. F. Li, R. H. Morris, Science, 2013, 342, 1080; vi S. A. M. Smith, R. H. Morris,
Synthesis, 2015, 47, 1775
Notes:
O33
Intercalation of Coordinatively Unsaturated FeIII Ion within
Interpenetrated MOF-5
Rebecca J. Holmberg, Thomas Burns, Samuel M. Greer, Libor Kobera, Sebastian A. Stoian,
Ilia Korobkov, Stephen Hill, David L. Bryce, Tom K. Woo, and Muralee Murugesu*
Despite the potential that has clearly been displayed by metal substitution within MOF-5, there
have not yet been any examples of metal addition to the structure outside of the Zn4O SBU. This
is a worthwhile endeavor, especially considering the already remarkable improvements to the
properties of MOF-5 that have been accessed through simple metal substitution.1 Thus, we set
out to explore the addition of a coordinatively unsaturated Fe III metal site to the framework. This
new structure, FeIII-iMOF-5,2 is the first example of an interpenetrated MOF linked through
intercalated metal ions. Structural characterization was performed with single-crystal and powder
XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which
reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer
spectroscopy confirmed that the intercalated ions were indeed FeIII, while DFT calculations were
employed to ascertain the unique pentacoordinate architecture around the FeIII ion. Interestingly,
this is also the first crystallographic evidence of pentacoordinate Zn II within the MOF-5 SBU.
This new MOF structure displays the potential for metal site addition as a framework connector,
thus, creating further opportunity for the innovative development of new MOF materials.
1 (a) Botas, J. A.; Calleja, G.; Sánchez-Sánchez, M.; Orcajo, M. G. Langmuir 2010, 26, 5300–5303.; (b) Brozek, C.
K.; Dincă, M. Chem. Sci. 2012, 3, 2110–2113.; (c) Brozek, C. K.; Dincă, M. J. Am. Chem. Soc. 2013, 135, 12886–
12891.; (d) Brozek, C. K.; Miller, J. T.; Stoian, S. A.; Dincă, M. J. Am. Chem. Soc. 2015, 137, 7495–7501.; (e)
Brozek, C. K.; Michaelis, V. K.; Ong, T.-C.; Bellarosa, L.; López, N.; Griffin, R. G.; Dincă, M. ACS Cent. Sci.
2015, 1, 252-260.
2 Holmberg, R. J.; Burns, T.; Greer, S. M.; Kobera, L.; Stoian, S. A.; Korobkov, I.; Hill, S.; Bryce, D. L.; Woo, T.
K.; Murugesu, M. J. Am. Chem. Soc. 2015, ja-2015-10584t.
Notes:
O34
Towards Modeling the Active Site of Photosystem II: New Structural
Motifs in Mn/Ca Chemistry from the Use of Salicylhydroxime
Alysha A. Alaimo,1 Simon J. Teat,2 George Christou,3 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; Advanced Light Source,
3
Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Department of Chemistry, University of
Florida, Gainesville, Florida, USA
Toward the synthesis of new structural models of the
oxygen-evolving complex (OEC) within Photosystem
II, some of the most crucial challenges to confront are:
(i) the Mn4Ca metal stoichiometry, (ii) the extended,
distorted cubane conformation, (iii) the stability of
high oxidation states for the Mn ions, and (iv) the
choice of the ancillary bridging ligand(s). With this in
mind, we have chosen to employ salicylhydroxamic acid (shaH2, Scheme
1), a photosynthetically effective group, as a means of obtaining new
molecular species containing both Mnn+ (n>2) and Ca2+.1 Ligand shaH2
can potentially undergo a metal-assisted amide-iminol tautomerism, and
thus transform to salicylhydroxime (shiH3); the latter is an oximate-based
ligand with four coordination sites available for binding to both high
oxidation state Mn and Ca2+ metal centers. We here present the synthesis,
structural, and physicochemical properties of a series of new
heterometallic Mn/Ca complexes with interesting topologies and novel
molecular motifs (Figure).
1
A. A. Alaimo, D. Takahashi, L. Cunha-Silva, G. Christou, Th. C. Stamatatos, Inorg. Chem. 54, 2137,
2015.
Notes:
O35
Synthesis and Biological Activity of Furan-Containing
Organoruthenium Complexes
Mohammadmehdi Haghdoost, Golara Golbaghi, and Annie Castonguay*
INRS-Institut Armand-Frappier, Laval, QC, Canada
Transition metal complexes have unique properties, notably due to their partially filled dorbitals, and can offer great opportunities to the field of chemotherapy, leading to the discovery
of new modes of action for therapeutics and novel interactions with biomolecules. Of particular
interest, ruthenium complexes display great advantages over platinum-based drugs that are
commonly use for cancer therapy. Our research aims at the discovery of novel multitasking
anticancer drug candidates, by combining ruthenium complexes and biologically active organic
molecules.
Numerous furan-containing compounds were reported to display anticancer, as well as antiinflammatory and antimicrobial activities. As an added value, the presence of a furan ring in the
backbone of inorganic complexes offers the unique possibility to link them to cancer cell
targeting agents or drug delivery systems via furan-maleimide Diels-Alder cycloadditions. This
type of linkage can then undergo thermal disassembly at physiological temperature, and allow
the release of furan-containing therapeutics.
The focus of this presentation will be on the synthesis and characterization of Ru(II)-arene
complexes with pendant furan arms, and our preliminary results regarding their in vitro
anticancer activity against human breast cancer cells.
Notes:
O36
Ligand Effects in Copper-Catalyzed Aerobic Oxygenation of Phenols
Laura Andrea Rodríguez Solano,1 Jean-Phlip Lumb,2 and Xavier Ottenwaelder1*
1
XoRG, Department of Chemistry and Biochemistry, Concordia University, Montreal, QC, Canada;
Department of Chemistry, McGill University, Montreal, QC, Canada
2
Tyrosinase is a ubiquitous copper-containing enzyme that converts phenols into ortho-quinones.
Its active site contains two His3-Cu centres that activate O2 in the form of a side-on peroxo
dicopper(II) species, P.1 Biomimetic studies have shown that polyamine ligands can control the
reactivity between Cu(I) and O2, favouring different coordination modes and CunO2 species.2
Recently, the Lumb group reported an efficient tyrosinase-like catalytic system capable of
converting phenols into ortho-quinones under aerobic conditions.4 Our mechanistic study
demonstrated the involvement of a P species in the catalytic cycle.5 The present work showcases
systematic variations of the ligand used in this catalytic system, with 4-tert-butylphenol as model
substrate. We correlate the catalytic
efficiency at room temperature with
the nature of the Cu2O2 species
forming at -80°C, and show that only
ligands that can accommodate a P
intermediate lead to decent catalysis.
We propose plausible grounds to
explain this correlation.
1.
2.
3.
4.
5.
Notes:
Solomon, E. I. et al. Chem. Rev. 114, 3659–3853 (2014).
Mirica, L. M., Ottenwaelder, X. & Stack, T. D. P. Chem Rev 104, 1013–1046 (2004).
Mirica, L. M. et al. Science 308, 1890–1892 (2005).
Esguerra, K. V. N., Fall, Y. & Lumb, J.-P. Angew. Chem. Int. Ed. 53, 5877–5881 (2014).
Askari, M. S., Esguerra, K. V. N., Lumb, J.-P. & Ottenwaelder, X. Inorg. Chem. 54, 8665–8672 (2015).
O37
1,2-Diphosphonium Dication : A Strong P-Based Lewis Acid in
Frustrated Lewis Pair Activations of B-H, Si-H, C-H and H-H Bonds
Julia M. Bayne, Michael H. Holthausen, Ian Mallov, Roman Dobrovetsky, and Doug W.
Stephan *
The heterolytic splitting of dihydrogen (H2) by main group frustrated Lewis pairs (FLPs) remains
a landmark achievement in Lewis acid and FLP chemistry. FLPs used for small molecule
activation typically exploit boranes, alanes, or tricoordinate carbon- or silicon-centered cations as
main group Lewis acids.1 Exploring electron deficient compounds of group 15, our group
demonstrated the remarkable catalytic activity of the highly electrophilic phosphorus cation
(EPC) [(C6F5)3PF]+ and the phosphonium dication [(SIMes)Ph2PF]2+ in a variety of Lewis acidmediated transformations.2 Although EPCs have been exploited as Lewis acid catalysts,
examples of P-based Lewis acids in FLP-type reactions are scarce. To this end, our group
reported the direct activation of H2 with a triphosphabenzene derivative3 and olefin
hydrogenation with the phosphonium cation [(C6F5)3PF]+ and sterically encumbered aryl
amines.4 In this presentation, the synthesis and reactivity of a robust and highly Lewis acidic 1,2diphosphonium dication [(C10H6)(Ph2P)2]2+ will be discussed. In combination with phosphorus
Lewis bases, the remarkable hydridophilicity of this dication was demonstrated through its
ability to activate B-H, Si-H, C-H and H-H bonds.5
(1) D. W. Stephan and G. Erker, Angew. Chem. Int. Ed., 2015, 54, 6400-6441. (2) J. M. Bayne and D. W. Stephan,
Chem. Soc. Rev., 2015, DOI: 10.1039/C5CS00516G. (3) L. E. Longobardi et al., J. Am. Chem. Soc., 2014, 136,
13453-13457. (4) T. vom Stein et al., Angew. Chem. Int Ed., 2015, 54, 10178-10182. (5) M. H. Holthausen, J. M.
Bayne, I. Mallov, R. Dobrovetsky and D. W. Stephan, J. Am. Chem. Soc., 2015, 137, 7298-7301.
Notes:
O38
Progress in Boro-cation Catalysis for Hydrofunctionalization
Patrick Eisenberger* and Cathleen M. Crudden*
Department of Chemistry, Queen's University, Kingston, ON, Canada
Cationic, 3-coordinate boron compounds have
recently stepped into the limelight as promising nonmetal-based Lewis acidic catalysts for organic
synthesis.[1] Here we present our progress in catalyst
design
using
meso-ionic
carbene-stabilized
borenium as well as DABCO-borenium ions for
mild hydrofunctionalization of unsaturated organic
molecules with hydrogen and borane.[2,3]
Mechanistic investigations suggest that both these
processes occur by distinctly different pathways
involving common motifs of Lewis-base supported
borenium-ions participating in bond activation and Lewis base supported boranes as the
reductant.
[1]
T. S. De Vries, A. Prokofievs, E. Vedejs Chem. Rev. 2012, 112, 4246. [2] P. Eisenberger, A. M. Bailey, C. M.
Crudden J. Am. Chem. Soc. 2012, 134, 17384. [3] P. Eisenberger, B. P. Bestvater, E. C. Keske, C. M. Crudden
Angew. Chem. Int. Ed. 2015, 54, 2467.
Notes:
P1
Complexation of Fe(II) and Fe(III) with the Tau Protein
Soha Ahmadi,1,2 Iraklii I. Ebralidze,1 Zhe She,1 and Heinz-Bernhard Kraatz*1,2
1
2
Canada; Department of Chemistry, University of Toronto, Toronto, ON, Canada
Tau is a protein that is associated with the stabilization of microtubules. A number of isoforms have been described
in the literature and all have binding domains that bind to microtubules. (1) Hyperphosphorylation of tau catalyzed
by protein kinases disrupts the interaction between tau and the microtubules, which in turn destabilizes the tubules
leading to decomposition into their building blocks a- and b-tubulins. (2) Hyperphosphorylation of tau then leads to
aggregation and formation of neurofibrillary tangles, one of the hallmarks of Alzheimer’s disease. Metal ions appear
to play a vital role and experimental results have shown increased levels of Fe, Cu, and Zn are associated with
neurofibrillary tangles. (3) Previously we have demonstrated that Cu(II) and Zn(II) can interact with tau and with
phosphorylated tau (p-tau) (4). Here we investigate the interaction of Fe(II) and Fe(III) with tau, p-tau and fragment
peptides in an effort to further our understanding of metal-tau interactions.
1. Frost, B., Götz, J., Feany, M.B. Connecting the dots between tau dysfunction and neurodegeneration . 2015, 25,
46-53;
2. Krüger, .L; Mandelkow, E.M. Tau neurotoxicity and rescue in animal models of human Tauopathies. Current
Opinion in Neurobiology. 2016, 36, 52-58;
3. Ayton S., Lei P., Bush A.L. Biometals and Their Therapeutic Implications in Alzheimer’sDisease.
Neurotherapeutics. 2015, 12, 109-120;
4. Martic, S.; Rains, M. K.; Kraatz, H.-B. Probing copper/tau protein interactions electrochemically. Anal. Biochem.
2013, 442, 130-137
P2
New Classes of Ferromagnetic Materials with Exclusively End-on Azido Bridges:
From Single- to 2D- Molecular Magnets
Dimitris I. Alexandropoulos,1 Luís Cunha-Silva,2 Albert Escuer,3 and Theocharis C. Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; REQUIMTE & Department of
3
Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; Departament de
Quimica Inorganica, Universitat de Barcelona, Barcelona, Spain
A new, flexible synthetic route which does not require the co-presence of
any organic chelating/bridging ligand but only the “key” precursor Me 3SiN3
has been discovered and led to a new class of inorganic materials bearing
exclusively end-on azido bridges; the reported 3d-metal clusters and
coordination polymers exhibit ferromagnetic, single-molecule magnetism
(Figure) and long-range magnetic ordering properties.1
[1] D. I. Alexandropoulos, L. Cunha-Silva, A. Escuer, and Th. C.
Stamatatos, Chem Eur. J., 2014, 20, 13860.
II
Figure. χM'' vs. T plot for a [Co 7]
complex discussed in this work.
P3
Synthesis and Characterization of a Family of [ReBr(CO)3(NN)]-Polyoxometalate
Covalent Hybrids
Thomas Auvray, Marie-Pierre Santoni, and Garry Hanan*
Département de chimie, Université de Montréal, Montréal, QC, Canada
The elaboration of hybrid systems combining the
intrinsic properties of its subcomponents is a widely
used approach in modern chemistry. Being interested
in the design of efficient light harvesting species to
convert solar energy into chemical energy, we decided
to combine the well-known [Re(CO)3Br(bpy)]
photosensitizer with polyoxometalates, a family of
anionic oxoclusters known for its electron reservoir
properties.1 A family of polypyridine ligands
covalently grafted on a Dawson type polyoxometalate
and its use as ligands to prepared the corresponding
Re(I) complex is presented.
1
M.-P. Santoni et al. , Dalton Trans., 2014, 43, 69906993
P4
Characterization of Cross-Coupling Reactions of Simple Iron Salts with Phenyl
Nucleophiles
Stephanie H. Carpenter and Michael L. Neidig*
Iron-catalyzed C-C cross-coupling systems have been known since the 1970s1, yet there is limited mechanistic
understanding of these systems. Simple iron salts are inexpensive and nontoxic, and are known to have short reaction
times and mild reaction conditions. Hence, simple iron salts are attractive starting materials for cross-coupling
systems. Previous work in the group involves the isolation and characterization of a homoleptic tetramethyliron(III)
ferrate complex from catalytically relevant iron salt, solvent, and methylmagnesium bromide. Further studies showed
the homoleptic tetramethyliron(III) ferrate complex to be an intermediate in the reduction pathway of FeCl3 and
MeMgBr. Current efforts are being placed on the isolation of intermediates formed during the reaction from simple
iron salts and various phenyl nucleophiles. Electron paramagnetic resonance (EPR) and Mössbauer spectroscopy have
shown the intermediates formed from simple iron salts and phenyl nucleophiles to be different from the methyl
reduction pathway.
1.
2.
Tamura, M.; Kochi, J. K. J. Am. Chem. Soc. 1971, 93, 1487.
Al-Afyouni, M. H.; Fillman, K. L.; Brennessel, W. W.; Neidig, M. L. J. Am. Chem. Soc. 2014, 136, 15457.
P5
d10 Nickel Difluorocarbenes and their Cycloaddition Addition Reactions with
Tetrafluoroethylene
Alex L. Daniels, Daniel J. Harrison*, Ilia Korobkov, and R. Tom Baker*
We report the first isolable nickel difluorocarbene complexes {NiP 2[P(OMe)3](=CF2); P2 = Ph2P(CH2)2PPh2 (1); P2
= 2 P(OMe)3 (2)}, which are also the only examples of formally d10 metal fluorocarbenes. These electron-rich
[Ni0]=CF2 complexes react with tetrafluoroethylene (TFE) to yield rare perfluorometallacyclobutanes [NiP 2(κ2CF2CF2CF2-), 3 and 4], with potential relevance to fluoroalkene metathesis and polymerization. Kinetic
experiments establish that the reactions of the new [Ni]=CF2 compounds with TFE are considerably faster than the
analogous reactions of their previously reported [Co]=CF2 counterparts. Further, we show that TFE addition to 2 is
a dissociative process, in contrast to [Co]=CF2, which reacts with TFE in an associative fashion. Finally,
preliminary reactivity of a [Ni](κ2-CF2CF2CF2-) complex (3) is described.
P6
Exploring the Water-Tolerance of Ruthenium Metathesis Catalysts
Adrian G. G. Botti and Deryn E. Fogg*
University of Ottawa, Centre for Catalysis Research and Innovation, Ottawa, ON, Canada
The dominant catalysts in current use for olefin metathesis are “second-generation” catalysts bearing an Nheterocyclic carbene (NHC) ligand, particularly the Grubbs and Hoveyda catalysts (Chart 1). These catalysts are
widely regarded as tolerant toward air and moisture. Indeed, Cazin and co-workers recently reported that turnover
numbers up to 7,000 could be attained in non-degassed solvents in RCM of a 1,1-disubstituted olefin using HII.1 On
deliberate addition of water, however, maximum conversions were halved. Here we explore the basis of this
behaviour, for both GII and HII. Specifically, we describe the impact of added water on catalytic productivity with
a more typical, ,-vinylic substrate; we examine reactions of the off-cycle species (precatalyst and resting state;
Chart 1) and active catalysts with water, with a particular focus on the nature of the side-products generated. Finally,
we also explore the stability of Ruthenium species potentially generated via reactions with water.
Chart 1. (a) The dominant olefin metathesis catalysts; (b) Mechanism highlighting key catalytic species studied for
GII.
(a)
(b)
[1] S. Guidone, O. Songs, F. Nahra, C. S. J. Cazin, ACS Catal. 2015, 5, 2697-2701.
P7
The Synthesis and Coordination Chemistry of 3,3’-Disubstituted-2,2’-Bipyridine
Ligands – Dimers, Trimers, Tetramers, and 1-D Chains
Marnie Edwardson, Nicholas J. Hurley, and Melanie Pilkington*
Bipyridines are a unique class of compounds that are very prevalent in the fields of surpramolecular and
coordination chemistry. Out of six possible regioisomers, 2,2’-bipyridine ligands are the most exploited. However,
examples of 3,3’-disubstituted-2,2’-bipyridines are less common and have not yet realized their full potential in the
field of coordination chemistry to date1.
In recent years we have pursued the synthesis and coordination chemistry of polydentate 3,3’-substituted-2,2’pyridine ligands (1)2 and (2)3 with appended pyridine and pyrazine heterocycles respectively. More recently we have
targeted the preparation of a new ligand (3) with appended oxadiazole-pyridyl heterocycles. The preparation of these
ligands together with magnetostructural studies of selected coordination complexes will be presented.
1
C.R. Rice, S. Onions, N. Vidal, J.D. Wallis, M.C. Senna, M. Pilkington, & H. Stoeckli‐Evans, Eur. J. Inorg.
Chem. 2002, 8, 1985-1997,2 N.J. Hurley, J.J. Hayward, J.M. Rawson, M. Murrie, & M. Pilkington, Inorg.
Chem. 2014, 53, 8610-8623, 3 N.J. Hurley, J.M. Rawson, & M. Pilkington, Dalton Trans. 2015, 44, 1866-1874.
P8
Synthesis and Reactivity of Phosphinimine Phosphine Staudinger Products
Louie Fan and Doug W. Stephan*
Frustrated Lewis pairs (FLP) have gained significant attention in the chemical community for their use in the metalfree activation of small molecules, such as H2, CO2, and NO. The premise for Lewis bases and Lewis acids to have
weakly or nonbonding interactions has been thoroughly investigated in both
inter- and intramolecular FLP systems. Recently, our group reported the
reactivity of various phosphinimine borane1 and borenium2 Staudinger
derived products for FLP-type chemistry.
In this work, borane-stabilized phosphorus azide, iPr2P(BH3)N3, is reacted
with a series of phosphorus alkynes, R12PCCR2 (R1 = t-Bu, iPr, Ph, R2 = Ph,
Cy, t-Bu), to generate a family of new phosphinime phosphine products
(Fig. 1). The preparation, characterization and reactivity of a series of
phosphinimine phosphine Staudinger products are explored herein.
1
R.L. Melen, A.J. Lough, D.W. Stephan,; Dalton Trans., 42, 8674-8683. 2M.H. Holthausen, I. Mallov, D.W.
Stephan,; Dalton Trans., 43, 15201-15211.
P9
Study of Bis-peptide Derivatives of Ferrocenoyl Histidine Including
Electrochemical and Metal Ion Binding Studies
Annaleizle Ferranco and Heinz-Bernhard Kraatz*
Canada
Zinc ions are essential for a variety of biological functions in proteins. In some case, Zn(II) plays a structural role,
while in others, it is the active site for a substrate transformation (references please). The most prevalent structural
motif has the Zn(II) in a tetrahedral coordination environment, ligated to the imidazole N in His, the thiolate S in
Cys or to carboxylate ligands of Asp or Glu. Research here focuses on the design of models for Zn-proteins and
other metalloproteins, where the ferrocene group is exploited as a structural scaffold that provides structural rigidity
for peptide residues and forces them into a conformation that is beneficial for metal coordination. Here we focus on
the use of His conjugates of ferrocene and the interaction of several ferrocenoyl histidine peptides was investigated
with a variety of divalent metal ions. Fc-peptide conjugates Fc[CO-His(Trt)-His(Trt)-OMe]2, Fc[CO-His(Trt)Glu(OMe)-OMe]2, and Fc[CO-His(Trt)-Glu(OMe)-OMe]2 were synthesized and observed to bind with metal ions
Zn2+, Cd2+, Cu2+, Ni2+, Mn2+, and Mg2+ in a 1:1 ratio. Interactions were monitored by 1H NMR spectroscopy and by
ESI-TOF-MS.
1.
2.
3.
Rebilly, J.-N.; Colasson, B.; Bistri, O.; Over, D.; Reinaud, O. Chem. Soc. Rev. 2015, 44, 467-489.
Daniel, A. G,; Farrell, N.P. Metallomics, 2014, 6, 2230-2241.
Laitaoja, M.; Valjakka, J.; Jänis, J. Inorg. Chem. 2013, 52, 10983-10991.
P10
Old Dog, New Tricks: Developing the Coordination Chemistry of
2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT)
Jamie M. Frost, Amélie Pialat, Damir A. Safin, and Muralee Murugesu*
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada
Owing to the presence of three fused terpyridine-like coordination pockets, 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine
(TPymT, Figure 1 left) is a highly attractive ligand for the synthesis of discrete clusters, coordination polymers and
Metal-Organic Frameworks (MOFs). Despite its potential, the coordination chemistry of TPymT is vastly
underdeveloped – which can principally be attributed to the
hydrolysis of the central triazine fragment, which readily
occurs under mild conditions. Thus, after first being
synthesised in 1959 it had only been used a handful of
times to synthesise coordination compounds until our
group began reinvestigating its chemistry in 2013.[1] This
poster details our recent progress in developing the
coordination chemistry of TPymT, with a particular focus
on Ag+ (Figure 1 right) and Fe2+/Fe3+ chemistry.
Figure. 1 Molecular structure of TPymT (left) and a
[Ag9TPymT4]9+ segment (right).
See; E. I. Lerner and S. J. Lippard, J. Am. Chem. Soc., 1976, 98, 5397; E. I. Lerner and S. J. Lippard, Inorg.
Chem., 1977, 16, 1537 and A. M. Garcia, D. M. Bassani, J.-M. Lehn, G. Baum and D. Fenske, Chem. Eur.
J., 1999, 5, 1234.
P11
Initial Employment of 3-Hydroxy-2-naphthohydroxamic Acid
in Mn and Mn/Dy Cluster Chemistry
Dimosthenis P. Giannopoulos,1 Luis Cunha-Silva,2 George Christou,3 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; REQUIMTE & Department of
3
Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; Department of
Chemistry, University of Florida, Gainesville, Florida, USA
The continuing interest in the synthesis and study of high-nuclearity transition
metal clusters in moderate-to-high oxidation states is driven by their
potentially interesting magnetic properties, including high-spin ground state
values (S) and single-molecule magnetism (SMM) behaviors.[1] Our group, and
others, has also had a longstanding interest in the synthesis of heterometallic
3d/4f SMMs, hoping that the co-presence of two different anisotropic and
high-spin metal ions within the same species will lead to SMMs with
unprecedented structural motifs, large energy barriers for the magnetization
reversal and blocking temperatures shifted to the liquid N 2 temperature
regime.[2] Towards this end, we turned our attention to the multidentate
chelating/bridging organic ligand 3-hydroxy-2-naphthohydroxamic acid
(nhaH2), a bulkier derivative of salicylhydroxamic acid, which has already
been successfully employed in 3d and 3d/4f metal cluster chemistry.[3] Herein,
we shall discuss our first results from the use of nhaH2 in Mn and Mn/Dy
cluster chemistry (Figure).
O
H
C
N
OH
OH
3-hydroxy-2-naphthohydroxamic acid (nhaH2)
Figure. (top) The ligand nhaH2, and (bottom) the
III
structure of a [Mn Dy ] cluster.
[1] G. Aromi and E. K. Brechin, Struct. Bonding (Berlin) 1997, 88, 1.
[2] Th. C. Stamatatos, S. J. Teat, W. Wernsdorfer and G. Christou, Angew. Chem. Int. Ed. 2009, 48, 521.
[3] M. R. Azar, T. T. Boron, J. C. Lutter, C. I. Daly, K. A. Zegalia, R. Nimthong, G. M. Ferrence, M. Zeller, J. W.
Kampf, V. L. Pecoraro and C. M. Zaleski, Inorg. Chem. 2014, 53, 1729.
P12
8
2
Ru(II) and Ru(III)-Anastrozole Anticancer Drug Candidates
Golara Golbaghi, Mohammadmehdi Haghdoost, and Annie Castonguay*
INRS-Institut Armand-Frappier, Laval, Quebec, Canada
Ruthenium complexes receiving increasing attention since antitumor agents NAMI-A and KP1019 successfully
entered phase II clinical trials. In comparison to various platinum compounds that are commonly used for cancer
therapy, ruthenium drug candidates are known to display a higher selectivity towards cancer cells, and to act via
different modes of actions, leading to fewer side effects and preventing the emergence of cancer cell resistance.
By combining cancer cell killing agents (ex: ruthenium) and cancer cell growth inhibitors (ex: Anastrozole), our
research aims at the discovery of superior anticancer therapeutics able to overcome the numerous problems
associated with existing chemotherapies. In this presentation, we will report the synthesis and the characterization of
a variety of Ru(II) and Ru(III)-Anastrozole complexes, as well as our preliminary results regarding their activity
against human breast cancer cells.
P13
Reactivity of Neutral Ligands Toward the Alkylidene Moiety of Grubbs-type
Olefin Metathesis Catalysts
Faidh Hana, Timothy G. Larocque, Anna C. Badaj, and Gino G. Lavoie*
Department of Chemistry, York University, Toronto, ON, Canada
Ruthenium alkylidene complexes are at the forefront of catalyst research due to the broad scope of possible olefin
metathesis transformations and substrates, including those with polar and protic functional groups. Studies of
decomposition pathways of these complexes are vital for designing catalysts with improved efficiency and lifetime.
Herein we discuss the sensitivity of the Ru=CHR active group to intramolecular insertions from “spectator” ligands.
The effect of the charge in ruthenium alkylidene complexes and the role of strong σ-donor weak π-acceptor
phosphaalkenes were investigated independently. Upon treatment of ruthenium alkylidene complex 1 with AgPF6,
dicationic ruthenium complex 2 was produced through nucleophilic attack from the N-heterocyclic carbene.1
Reaction of phosphaalkene 3 with RuCl2(PCy3)2(CHPh) produced complex 4, which also results from a migratory
insertion of the phosphaalkene into the benzylidene followed by two C-H activation.2 These findings provide
important insights for designing the next generation of ruthenium-based olefin metathesis catalysts.
(1) Larocque, T. G.; Badaj, A. C.; Lavoie, G. G. Dalton Trans. 2013, 42, 14955–14958.
(2) Larocque, T. G.; Lavoie, G. G. New J. Chem. 2014, 38, 499.
P14
Ring-Size Effects on Structures and Properties of Benzo-fused Dithiazolyl
Radicals
Mohamad Harb, Natalia Mroz, Yassine Beldjoudi, and Jeremy Rawson*
Sulfur-nitrogen free radicals have been developed in the design of both organic
magnets and conductors. This poster will examine the effects of increasing the ring
size (n = 1 – 3) on a series of benzo-fused dithiazolyls (1). The synthetic
methodology, structures and magnetic properties of these derivatives will be
discussed.
.
( )n
1
P15
Base Metal and Ruthenium Catalysts for the Synthesis of 1-butanol via the
Guerbet Reaction
Cassandra E. Hayes,1,2 R. Tom Baker,1* and William D. Jones2*
1
2
Department of Chemistry, University of Ottawa, Ottawa, ON, Canada; Department of Chemistry,
University of Rochester, Rochester, NY, USA
The development and widespread use of biofuels as replacements for traditional petrochemical fuels is an important
and growing issue to the global economy and environment. Current technologies cite ethanol as the most accessible
renewable fuel source; however, its use comes with a significant list of drawbacks. As such, ready access to so
called “advanced biofuels” (e.g. n-butanol) has become a topic of increasing interest to researchers. The
homologation of ethanol via the Guerbet process (figure) provides a renewable means of accessing n-butanol.
Herein we demonstrate the use of iron,
cobalt, and ruthenium dehydrogenation
catalysts for their use in the Guerbet
process. Initial catalytic studies show
that iron and cobalt catalysts catalyse
the Guerbet reaction with a high
selectivity for the formation of nbutanol over other longer chain byproducts.
P16
Synthesis and Characterization of Heteroleptic Copper(I) Complexes
for Light Harvesting Applications
Jennifer Huynh, Paloma Prieto, Jeanette A. Adjei, and Bryan D. Koivisto *
Department of Chemistry and Biology, Ryerson University, Toronto ON, Canada
The dye sensitized solar cell (DSSC, or Grätzel cell) is a next generation photovoltaic device that shows remarkable
potential for solar energy markets. The powerhouse of the DSSC is the dye molecule, which has the ability to
harvest light, and convert it into electrical current. Inorganic dyes such as zinc porphyrins and ruthenium(II)
complexes have drawn much attention for their high efficiencies, but heteroleptic tetrahedral copper(I) complexes
are a viable alternative owing to their substantially lower cost and opportunity for development. The main challenge
for using tetrahedral Cu(I) dyes is their energetically favourable distortion to a square planar Cu(II) geometry upon
oxidation. To prevent this, phenanthroline-based ligands are particularly attractive due to their rigid bidentate
structure, while functionalizing at the 2,9- positions on the phenanthroline ligand creates a steric environment
preventing geometric distortion (Figure 1). This presentation will focus on recent efforts towards the synthesis and
characterization of novel ligands and heteroleptic copper(I) complexes for light-harvesting applications.
Figure 1. Targeted motif of the Cu(I) complex dye molecule explored in this study.
P17
Inclusion Chemistry of 4-Phenyl-1,2,3,5-Dithiadiazolyl Radical in MIL-53(Al)
Erika M. Haskings and J.M. Rawson*
The interactions and applications of host-guest chemistry have generated considerable interest in recent years, with
the nature of the host···guest interaction leading to effects in which the host can modify the guest properties or
reactivity or, conversely, the guest affects the host structure. This poster will describe the inclusion chemistry of 4phenyl-1,2,3,5-dithiadiazolyl (PhDTDA) radical in the host metal-organic framework MIL-53(Al).
DTDA radicals tend to dimerise in the solid state but undergo monomer-dimer equilibria in solution. In this context
we have been interested to examine how the host affects the monomer-dimer equilibrium and chemical reactivity of
the radical. The PhDTDA radical was incorporated into the porous framework via gas phase diffusion and led to a
colour change of the host from white to red. Powder X-ray diffraction studies and
DSC studies revealed that the radical was included into the framework while solid
state EPR studies indicated low radical concentrations indicating a dimerization can
occur within the host cavities. The reactivity of the radical within the host-guest
framework will be discussed.
Figure 1: 4-Phenyl-1,2,3,5-dithiadiazolyl (PhDTDA) radical
P18
Design and Synthesis of Lanthanide Single Molecule Magnets using the Schiff
Base Approach
Thomas Lacell, Gabriel Brunet, Amélie Pialat, Rebecca J. Holmberg, Wolfgang Wernsdorfer, Ilia Korobkov, and
Muralee Murugesu*
Isostructural complexes of the formula [Ln4(H2htmp)4(MeOH)8](NO3)3(OH)·5MeOH·0.5H2O (Ln = GdIII 1, DyIII 2)
were synthesized using a new Schiff base ligand, abbreviated H 4htmp. Compound 2 exhibits ferromagnetic
exchange coupling under zero dc field with a large thermal relaxation barrier of Ueff = 158 K. To the best of our
knowledge this barrier is the sixth largest reported barrier for Schiff base complexes to date. The effect of the
bridging tetrazine ring on the magnetic exchange interactions is explored through structural and magnetic studies.
P19
Covalent Organic Frameworks: Using 2D Rigid Cores for Enhanced
Electron/Charge Transport
Andrew Hollingshead, François Magnan, and Jaclyn Brusso*
Covalent Organic Frameworks (COFs) represent a relatively new class of crystalline porous materials that have
emerged as a novel strategy in the design of new functional materials. This may be attributed to their atomically
precise integration of building blocks into 2D or 3D topologies, which are characterised by lightweight elements,
strong covalent bonds, high specific surface area, defined pore size and great structural diversity. As a result, since
the first reported COF in 2005,1 a great deal of research has focused on their development for use in a variety of
applications such as catalysis, gas storage, drug delivery, chemical sensing and organic electronics. In regards to the
later, the designability of building blocks to develop robust porous
networks that feature 2D extended organic sheets with layered stacking
structures in which periodic columnar π-arrays and ordered 1D channels
are generated is particularly attractive. Our approach to COFs involves
the use of heteroaromatic building blocks where the π-conjugation can
be extended through various aromatic “linkers” (e.g. benzene vs.
naphthalene vs. anthracene). This extension of π-conjugation is
anticipated to enhance the charge transport properties while creating a
new family of semi-conductive materials. Preliminary work towards the
development of monomers 1 and 2, and their implementation into COFs,
will be presented.
1. Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Science 2005, 310 (5751),
1166-1170.
P20
Reactivity of Iron Complexes of a Radical o-Phenylenediamine-based Ligand
Trevor Janes, Pavel Zatsepin, and Datong Song*
Department of Chemistry, University of Toronto, Toronto ON, Canada
One of inorganic chemistry’s current goals is to exploit the ability of certain ligands to exist in multiple oxidation
states. Ideally, such ligands will work in concert with metals to accomplish challenging multielectron redox
transformations. In particular, o-phenylenediamine-derived ligands have received
attention for their capability as electron reservoirs. 1 Our research group has
investigated the coordination chemistry of a sterically bulky o-phenylenediamide (L2-)
towards Fe2+; we have observed its readiness to oxidize into the odiiminosemiquinonate (L-) form depicted in Figure 1.2 This poster presentation will
detail our application of the π-delocalized radical L- as a spectator ligand to sponsor
redox processes, facilitate N-group transfer, and stabilize three-coordinate iron.
Figure 1. Bulky o-diiminosemiquinonate (L-)
1. Broere, D. J., Plessius, R., van der Vlugt, J. I., Chem. Soc. Rev., 2015, 44, 6886-6915.
2. Janes, T., Rawson, J. M., Song, D., Dalton Trans., 2013, 42, 10640-10648.
P21
Asymmetric Hydrogenation by NHC-stabilized Borenium Ion Catalysis
Jolie Lam and Douglas W. Stephan*
Amines and their derivatives are synthetically
important compounds with a wide range of
applications, varying from dyes to pharmaceuticals.
In
particular,
potential
pharmaceutical
intermediates and targets are required in high
enantiopurity, which is typically achieved by chiral
transition metal-mediated transformations.1 Nheterocyclic carbene (NHC)-stabilized borenium
ions2 have recently been reported to be excellent
metal-free catalysts for the hydrogenation of
imines under mild conditions by Stephan and coworkers. We are now targeting the syntheses of new borenium ions
that incorporate chiral substituents for the enantioselective hydrogenation of prochiral imines. Borenium cations
stabilized by chiral bisoxazoline3 carbenes were synthesized and preliminary results show excellent catalysis with
high conversions. Simultaneously, we are tuning the Lewis acidity and selectivity of these systems by exploiting
variations of the borane to enhance reactivity.4 The efficacy of these systems in the asymmetric catalytic reduction of
ketimines will be discussed.
1.
2.
3.
4.
Fleury-Brégeot, N.; Fuente, V.; Castillón, S.; Claver, C. ChemCatChem. 2010, 2, 1346-1371.
Farrell, J. M.; Hatnean, J. A.; Stephan, D. W.. J. Am. Chem. Soc. 2012, 134, 15728-15731.
Lindsay, D. M.; McArthur, D. Chem. Commun. 2010, 46, 2474-2476.
Farrell, J. M.; Posaratnananthan, R. T.; Stephan, D. W. Chem. Sci. 2015, 6, 2010-2015.
P22
Nickel(Ⅱ) and Palladium(Ⅱ) Complexes of Perimidine-based Carbene Ligands:
Catalysis for C-N Coupling
Sojung Lee, T.-G. Ong, E. Perron, I. Korobkov, and Darrin Richeson*
The discovery of stable diaminocarbenes as well as their application as ligands for transition metals has had a
tremendous impact on the field of homogeneous catalysis. In this regard, we have designed novel perimidine-based
diaminocarbenes as ligands. These ligands have unique steric and electronic features. The Nickel (0), Nickel(Ⅱ) and
Palladium(II) complexes of these carbene ligands have been synthesized and details of their characterization will be
presented. Our initial efforts to exploit the unique properties of these carbenes and to reveal their potential in metal
catalyzed transformations will be described. For example, the Ni complexes have been found to have oxidative
addition of aryl iodide and fluorinated pydridine and the Pd complexes are active catalysts for C-N bond formation.
P23
Thieno[3,2-b]thiophene-based Building Blocks for the Construction of 2D
Thienoacenes
François Magnan and Jaclyn Brusso*
Molecular electronics offer an enticing alternative to traditional silicon-based semiconductors, owing in large part to
their ease of fabrication and the associated lowered cost of production. Device stability and performance remain,
however, major limitations toward more generalized applications. And while charge mobility generally increases
upon extension of the conjugation, stability toward oxidation will usually decrease upon doing so. Incorporation of
heteroatoms, such as sulphur, in the polycyclic framework has been shown to be a viable strategy to address both of
these issues. Concurrently, larger orbitals on the
heteroatoms promote π- π stacking and efficient
molecular overlap in the solid-state, a non-trivial factor
in the performance of semiconductors. To this end, our
group has focused on 2D thienoacenes (1, 2) as a way of
extending the effective conjugation, thus enhancing the
optoelectronic properties of the molecules. This
presentation will focus on current efforts toward the
integration of fused thiophenes systems as further ways
of fine tuning the molecular properties.
P24
Friedel-Crafts Reactivity of a Highly Lewis Acidic Phosphonium Catalyst
Towards Benzyl Alcohols and Benzyl Ethers
James H. W. LaFortune, Jiantao Zhu, and Douglas W. Stephan*
The Fridel-Crafts reaction, wherein a Lewis or Brønsted acid catalyzes carbon-carbon bond formation, endures as
the preferred method of arene and heteroarene alkylation in many industries since its discovery in 1887. Over the
past several decades, significant efforts have been made to lower catalyst loadings and expand the substrate scope.
While catalytic Fridel-Crafts alkylations with benzylic alcohols are well known, alkylations with benzylic ethers are
less common. Furthermore, these reactions generally require high catalyst loadings of 5 to 10 mol%. 1 Recently, we
have developed a new class of Lewis acids based on highly electrophilic phosphonium cations. These species have
been shown to be highly reactive, facilitating these reactions with low catalyst loadings. 2 In this poster we explore
the reaction of these Lewis acids towards Friedel-Crafts alkylations with benzylic alcohols and ethers.
1 Reuping, M.; Nachtsheim, B. J.; Beilstein Journal of Organic Chemistry, 2010, 6, 6, doi:10.3762/bjoc.6.6.
2 Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W.; Science. 2013, 341, 1374. Pérez, M.; Hounjet, L.
J.; Caputo, C. B.; Dobrovetsky, R.; Stephan, D. W.; J. Am. Chem. Soc. 2013, 135, 18308.
P25
Stereochemical Reactivity of the Schiff Base Ligand
N-salicylidene-2-aminocyclohexanol in Lanthanide Chemistry
Eleni C. Mazarakioti,1 Katye M. Poole,2 Luís Cunha-Silva,3 George Christou,2 and Theocharis C. Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; Department of Chemistry,
3
University of Florida, Gainesville, Florida, USA; REQUIMTE & Department of Chemistry and
Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal
The employment of the cis-/trans-mixture of the Schiff base ligand
N-salicylidene-2-aminocyclohexanol, as well as its pure transanalogue, in lanthanide cluster chemistry has afforded complexes
with different nuclearities (Figure), indicating the stereochemical
effect of the ligand in the structural identity of polynuclear
compounds. Magnetic and optical studies revealed single-molecule
magnetism and photoluminescence behaviors for all the reported
compounds.1 The organic precursors of this work can be considered
as promising ligands for the construction of dual-acting molecular
species with potential applications in the field of molecule-based
electronics.
1
E. C. Mazarakioti, K. M. Poole, L. Cunha-Silva, G. Christou, Th.
C. Stamatatos, Dalton Trans., 2014, 43, 11456.
P26
Figure. The structure of one of the Ln8
clusters discussed in the present work.
Decomposition of Phosphine-Functionalized Metathesis Catalysts by Lewis
Donors: Generality and Implications
William L. McClennan, Justin A. M. Lummis, and Deryn E. Fogg*
Olefin metathesis is a powerful tool for the assembly of carbon-carbon double bonds. With industrial processes
beginning to emerge for the molecular metathesis catalysts, improved understanding of their decomposition
pathways is becoming increasingly important. We recently described “donor-induced decomposition” of the firstgeneration Grubbs catalyst RuCl2(PCy3)2CHPh GI.2 Rapid degradation in the presence of pyridine occurred via a
key σ-alkyl species which was intercepted and characterized by NMR and X-ray analysis.1 Here we provide
evidence that the second-generation Grubbs methlyidene resting states GIIm follow a closely related pathway that is
much faster than degradation of complexes in the absence of pyridine. We also demonstrate that this pathway is
general for Lewis donors with widely ranging basicity and show the impact of this pathway during catalysis with
various phosphine-functionalized Grubbs type catalysts. These findings have important implications for the
productivity of Grubbs-class metathesis catalysts.
(1) Lummiss, J. A. M.; McClennan, W. L.; McDonald, R.; Fogg, D. E. Organometallics 2014, 33, 6738-7741.
P27
Main Group Compounds Supported by an NHC Carbene Borate
Tho Nguyen and Georgii I Nikonov*
N-heterocyclic Carbene (NHC) ligands are ubiquitous in stabilising a variety of transition-metal complexes and find
numberless applications in catalysis. More recently, NHC ligands became popular also in main group chemistry and,
in particular, showed promise in the stabilization of low oxidation state main-group compounds.1-4 In this study, the
anionic NHC/borate ligand [(C6F5)3BCHC{N(2,6-Pri2C6H3)}2C:]-.Li+(THF)2 is employed for preparation of a series
of main group element compounds of Si, Ge, B and Zn. Furthermore, the latter can be converted into a Zn-hydride
complex which is being tested in catalytic hydrosilylation and hydroboration.
1. B. Kinjo, B. Donnadieu, M. A. Celik, G. Frenking, G. Bertrand, Science 2011, 333, 610.
2. K. C. Mondal, H. W. Roesky, M. C. Schwarzer, G. Frenking, B. Niepötter, H. Wolf, R. Herbst-Irmer, D. Stalke,
Angew. Chem., Int. Ed. 2013, 52, 2963.
3. Y. Li, K. C. Mondal, H. W. Roesky, H. Zhu, P. Stollberg, R. Herbst-Irmer, D. Stalke, D. M. Anrada, J. Am.
Chem. Soc. 2013, 135, 12422.
4. Y. Xiong, S. Yao, S. Inoue, J.D. Epping, M. Driess, Angew. Chem., Int. Ed. 2013, 52, 7147.
P28
Tandem Catalysis for Water Splitting
Virginie Peneau, Nick Alderman, and Sandro Gambarotta*
Photocatalytic water splitting is a promising area for the production of hydrogen and oxygen. However, problems
arise with the separation of the mixture of gasses produced, adding large expenses to any commercialised systems.
An attractive proposal is to find a water splitting system involving a shuttle, such that the two gasses are released at
separates points in the cycle, negating the gas separation problem.
This study focuses on the separate production of oxygen and hydrogen from water splitting using tandem catalysis
from carriers that are able to be readily oxidised and reduced.
Two routes are considered; organic and inorganic carriers. Quinone/ benzoquinone is a bio-inspired organic carriers.
Quinone complexes are used by plants to store hydrogen and it has already been shown that quinone can be reduced
and oxidised using various catalyst or electrolysis. Inorganic carriers such as heteropolyacid complexes have shown
promising results using electrolysis. Silicotungstic acid complex was used as hydrogen and electron carrier from
water splitting. In a separate vessel hydrogen was released using platinum catalyst. 1
The combination of photoactive species such as TiO2 base catalyst, bismuth, vanadate, and cobalt able to reduce or
oxidise water with to these carriers is investigated.
Water oxidation mediated by a photosensitiser [Ru(bpy) 3]2+ persulfate system is a known reaction using persulfate
as a sacrificial electron acceptor. The role of the carriers is to capture hydrogen and electrons. Another investigation
is the use of the previous carriers instead of persulfate with photosensitiser to allow the storage of hydrogen.
P29
Nickel(II) Clusters with Ferromagnetic and Emissive Properties from the Use
of a New Fluorescent Schiff Base Ligand
Panagiota S. Perlepe,1 Luís Cunha-Silva,2 Kevin Gagnon,3 Simon J. Teat,3 Albert Escuer,4 and Theocharis C.
Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada, REQUIMTE & Department
3
of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal , Advanced
4
Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA, Departament de Quimica
Inorganica, Universitat de Barcelona, Barcelona, Spain
The choice of the organic chelating/bridging ligand is currently one of the most
appealing chalenges towards the synthesis of new polynuclear 3d-metal complexes
with diverse physical properties, such as magnetism, optics, conductivity and catalysis.
In this work, we present the initial employment of the fluorescent bridging ligand Nnaphthalidene-2-amino-5-chlorobenzoic acid in Ni(II) cluster chemistry.1 Two new
Ni12 and Ni5 clusters with wheel-like and molecular-chain topologies, respectively,
were synthesized; the nature of the ligand has allowed unexpected transformations to
occur, as well as ferromagnetic and emission behaviors to emerge.
[1] P. S. Perlepe, L. Cunha-Silva, K. Gagnon, S. J. Teat, A. Escuer and Th. C.
Stamatatos, submitted to Chem. Eur. J.
Figure. Complete structure of the Ni12
wheel compound.
P30
A New Homogenous Tetradentate Ruthenium-Based Catalyst for the
Hydrodeoxygenation of Biomass-Derived Substrates in Aqueous Acidic Media
Konrad Piaseczny, Ryan Sullivanm and Marcel Schlaf*
Throughout the past century fossil fuels such as crude oil and natural gas have dominated the production of fuels and
petrochemicals. However, the use of these fossil-derived fuels has well-established negative environmental effects.
A shift to lignocellulosic biomass as a renewable carbon feedstock is therefore desirable, but also challenging as this
carbon source is characterized by an overfunctionalization with highly reactive hydroxyl and other oxygen groups.
This problem can however in principle be overcome through the use of catalytic hydrodeoxygenation reactions that
reject oxygen as water. This project focuses on the evaluation of trans-[Ru(2,9-di-(pyrid-2’-yl)-1,10phenanthroline)(NCMe)2](OTf)2 as a homogeneous, hydrogenation catalyst postulated to be stable at the required
high temperatures (≥ 175 °C) due to tetradentate chelation by the highly robust 2,9-di-(pyrid-2’-yl)-1,10phenanthroline ligand. Complexation (see below) gives the ruthenium complex, trans-[Ru(2,9-Di-(pyrid-2’-yl)-1,10phenanthroline)(NCMe)2](OTf)2 in 86 % yield in
high purity. In preliminary test the catalysts
realizes the hydrogenation (175 °C, 800 psi H2,
H2O) of 2,5-hexandione, which forms part of a
value chain from cellulose to hexane, to 2,5hexandiol and 2,5-dimethylfuran in > 90 % yield
without apparent decomposition.
P31
Toward the Development of New Energetic Ionic Liquids as Green Hypergolic
Fuels
Amélie Pialat,a Anguang Hu,b and Muralee Murugesu*,a
a
b
Department of Chemistry, University of Ottawa, Ottawa, ON, Canada; Defense R&D Canada-Suffield
Research Centre, Medicine Hat, AB, Canada
Rocket propulsion is due to the spontaneous ignition of hypergolic
fuels upon contact with oxidants inside a combustion chamber.1
This reaction generates important volumes of hot gases creating
thrust. Current propellant systems mainly use hydrazine and its
methylated derivatives as hypergolic fuels however, they are
highly volatile and carcinogenic. For this reason, during the last
decade, the unique properties of ionic liquids; low vapour pressure,
high thermal stability, low flammability and high designability
have considerably drawn attention in the research for new green
hypergolic fuels.2 In this poster, the design, synthesis and study of
the energetic properties of a new family of cyanoborohydridebased ionic liquids will be presented.
[1] : Holtzmann, R. T. Chemical Rockets 1969, Marcel Dekker, New York.
[2] : Zhang, Q.; Shreeve, J. M. Chem. Rev. 2014, 114, 10527-10574.
P32
Metal Adamantyls; Synthesis and Reactivity
Kamalpreet Singh, Fioralba Taullaj, David Armstrong, and Ulrich W. Fekl *
Department of Chemistry, University of Toronto Mississauga, Mississauga, ON, Canada
Since its discovery in 1933, adamantane has been at the forefront of
research in cage compounds.1,2 The diamondoid structure of
adamantane gives it unique properties for use in pharmaceuticals,
advanced materials, and catalysis. This versatility led to rigorous
investigation of the compound’s reactivity. The majority of the
chemical transformations affecting adamantane have been limited to
oxidations and halogenations, and very limited progress has been
made in the synthesis of higher diamondoids.2,3 Our research aims to
expand the scope of potential adamantane reactivity by developing
novel metal based adamantyl complexes and exploring the subsequent
reactivity of such compounds. The synthesis and reactivities of a
number of new organometallic adamantyl complexes will be
discussed.
1
Fort, R. C.; Schleyer, P. von R. Adamantane: Consequences of the Diamondoid Structure. Chem. Rev. 1964, 64
(3), 277.
2
V V Sevost’yanova and Mikhail M Krayushkin and A G Yurchenko. Advances in the Chemistry of Adamantane.
Russian Chemical Reviews 1970, 39 (10), 817.
3
Schwertfeger, H.; Fokin, A. A.; Schreiner, P. R. Angew. Chem. Int. Ed. 2008, 47, 1022-1036.
P33
A Homogeneous Ruthenium Catalyst Based on a Tetradentate Pyridine-Aniline
Ligand for the Hydrodeoxygenation of Biomass Derived Substrates to ValueAdded Chemicals in Aqueous Acidic Media
Maryanne Stones, Konrad Piaseczny, Ryan Sullivan, and Marcel Schlaf*
The catalytic hydrodeoxygenation of biomass can
in principle provide renewable carbon feedstocks
that can replace or reduce the use of fossil carbon
sources in industrial applications. However, the
development of catalysts that are stable in
aqueous acidic media and at high temperatures,
and exhibit promiscuous catalytic activity
towards the hydrodeoxygenation of biomass
derived substrates is a currently unresolved
challenge. This project focusses on the synthesis of a homogeneous catalyst based on a tetradentate nitrogen-donor
ligand containing a rigid benzene backbone and pendant pyridine groups. Following literature procedures, the ligand
N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine was synthesized in 40 % yield. A ruthenium complex intermediate
[Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(Cl)-(DMSO)](Cl) was prepared in 95 % yield. Metathesizing
chloride for labile aceto- or benzo-nitrile ligands with AgOTf at elevated temperatures, two potential catalysts were
synthesized from this intermediate. Preparative scale up of [Ru(N,N'-Bis-(2-pyridylmethyl)-ophenylenediamine)(NCMe)2](OTf)2 required high-pressure and proved difficult. The preparation of the alternative
complex [Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(NCPh)2](OTf)2 at ambient pressure allowed
structural characterization by mass spectrometry and NMR spectroscopy, but again preparation on an experimentally
and practically viable scale, as well as purification, is pending optimization of the preparative protocol.
P34
Reactivity of Aryloxo Vanadium(III) and (IV) with Carbon Dioxide
Camilo Viasus, Nick Alderman, and Sandro Gambarotta*
Activation of small molecules like carbon dioxide by metal complexes is a great challenge due to the high
thermodynamic stability of CO2. If metal complexes are capable to afford deoxygenation or disproportionation,
these transformations may be attractive and useful as long as the process is catalytic. When a M-O function is
formed as a by-product instead, the reaction can be only stoichiometric. Nevertheless, when the transfer is limited to
one electron, radical behavior might be triggered. In this work we are modulating the one or two electron transfer
using vanadium(III) and (IV) compounds. We will present the possibility to switch from deoxygenation to radical
behavior to form organic esters.
P35
Alkynyl-Based Fluorophosphonium Lewis Acids
Alexander Waked and Douglas W. Stephan*
Many industrial and pharmaceutical processes, such as hydrogenation and hydrosilylation, are catalyzed by
transition metal-based systems. While these catalysts efficiently mediate these reactions, the dependence on precious
metals, environmental impact, and high cost have led to increased interest in developing metal-free alternatives.
Previous research in the Stephan group has shown that fluorophosphonium cations act as bulky Lewis acids and can
catalyze hydrosilylation and hydrodefluorination reactions. 1,2 The current study presents the synthesis of various
alkynyl fluorophosphonium systems. These species provide interesting avenues to the modification of the Lewis
acidity at phosphorus and thus offer unique approaches to new catalytic activity of fluorophosphonium compounds.
1. Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W., Science (Washington, DC, U. S.) 2013, 341
(6152), 1374-1377.
2. Holthausen, M. H.; Mehta, M.; Stephan, D. W., Angew. Chem., Int. Ed. 2014, 53 (25), 6538-6541.
P36
Enantiomerically Pure Bidentate Amine Tethered N-heterocyclic Carbenes:
Synthesis, Transition Metal Complexes and their Asymmetric Catalytic
Applications
Kai Y. Wan, Alan J. Lough, Heiko Rebmann, and Robert H. Morris*
Certain precious metal complexes are efficient catalysts for the asymmetric hydrogenation (AH) of ketones and
imines into their corresponding enantiopure alcohols and amines, respectively. These products have wide industrial
applications, especially in the pharmaceutical industry. The AH catalysts, however, contain toxic and expensive
metals and potentially harmful and air-sensitive phosphorus ligands. As a consequence, the development of effective
catalysts based on benign, abundant metals such as iron1 and ligands based on organic compounds, such as NHC
would provide a significantly greener approach for AH. 2,3 In this presentation, we will discuss our recent
development of new chiral NHC ligands that bear primary amine donors starting from chiral aminoalcohol
precursors. This class is highly flexible due to handy electronic modification at the NHC component and steric
modification on the backbone and NHC substituents. Moreover, the amine moiety can contain a third donor
substituent that results in a highly rigid pincer-type ligand structure. During the talk, we will focus on the
coordination chemistry of this class of ligand on transition metals, especially iron. The second part of the talk will be
on the potential applications of this ligand in asymmetric hydrogenation.
1. Lagaditis P., Sues P., Sonnenberg J., Wan K., Lough A., Morris R., J. Am. Chem. Soc., 2014, 136, 1367–1380
2. O, W. W. N.; Lough, A. J.; Morris, R. H. Chem. Commun. 2010, 46, 8240.
3. O, W. W. N.; Morris, R. H. ACS Catal. 2012, 3, 32.
P37
Magnetic Circular Dichroism Studies of Iron-bound Human Calprotectin
Tessa M. Woodruff, Toshiki G. Nakashige, Elizabeth M. Nolan, and Michael L. Neidig*
Magnetic Circular Dichroism
CP-Ser/Fe(II)
De (M -1 cm-1)
2.0
1.6
1.2
0.8
0.4
0.0
DHis Asp-CP/Fe(II)
2.0
3
1.6
1.2
-1
-1
De (M cm )
Calprotectin (CP) is a metal-sequestering protein found in large
quantities at sites of infection. It is believed that CP prevents
microbial infections by withholding the metal ions needed for
microbial replication and colonization. It has been shown that human
CP binds manganese, iron and zinc. From other studies, it has been
shown that CP also binds iron at its His4/His6 site, an unusual metal
binding site. Here, near-infrared magnetic circular dichroism (MCD)
studies are presented, which permit the evaluation of the coordination
number and geometry of iron(II)-bound CP and its comparison to
well studied iron(II) metalloenzymes containing the common 2-His1-carboxylate facial triad iron-binding site. Both first coordination
sphere and distal site mutants are evaluated in order to further probe
iron binding in CP to confirm that iron(II) is bound in a distortedoctahedral geometry at the His4/His6 site.
0.8
0.4
0.0
6
8
10
12
3
14
16
-1
Energy (10 cm )
P38
Synthesis and Properties of BN-Heterocycles
Dengtao Yang and Suning Wang*
Among π-conjugated organoboron compounds, BN imbedded aromatic molecules have attracted much research
interest and efforts.1The replacement of a C-C unit in an aromatic molecule with an isoelectronic B-N unit could
lead to distinct changes in its electronic, photophysical, and chemical properties. However, the syntheses of BN
substituted polycyclic aromatic hydrocarbons are in general very challenging.
In 2013, our group reported a photoelimination reaction involving BN-heterocycles.2 The elimination products are
highly luminescent and can be used as emitters in optoelectronic devices. Very recently we further investigated the
elimination of these kinds of BN-heterocycles via thermal pathways3 as well as in electroluminescent (EL) devices4.
(1) Campbell, P. G.; Marwitz, A. J. V.; Liu, S.-Y. Angew. Chem. Int. Ed.2012, 51, 6074.
(2) Lu, J. S.; Ko, S. B.; Walters, N. R.; Kang, Y.; Sauriol, F.; Wang, S. Angew. Chem. Int. Ed.2013, 52, 4544.
(3) Yang, D.-T.; Mellerup, S. K.; Wang, X.; Lu, J.-S.; Wang, S. Angew. Chem. Int. Ed.2015,54, 5498.
(4) Wang, S.; Yang, D.-T.; Lu, J.; Shimogawa, H.; Gong, S.; Wang, X.; Mellerup, S. K.; Wakamiya, A.; Chang, Y.L.; Yang, C.; Lu,Z.-H. Angew. Chem. Int. Ed.2015,DOI : 10.1002/anie.201507770.
P39
Converting Amines and Alcohols into Amides or Imines
Matthew Yosurack and Dmitry G. Gusev*
Department of Chemistry, Wilfrid Laurier University, Waterloo, ON, Canada
PNP and NNP osmium complexes from our laboratory[1,2]
catalize dehydrogenative coupling of alcohols and amines to
give imine and amide products, respectively, at 25 – 80 °C,
while using 0.05 – 0.2 mol% [Os].
[1] Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.;
Denis Spasyuk, D.; Gusev, D. G. Organometallics
2011, 30, 3479-3482.
[2] Spasyuk, D.; Vicent, C.; Gusev D. G. J. Am. Chem. Soc.
2015, 137, 3743-3746.
P40
Figure. Dehydrogenative coupling of primary
alcohols and amines.
Water-soluble Platform for Selective Fe(II), Fe(III), Ru(III) and Zn(II) Detection
Nadia O. Laschuk and Olena V. Zenkina*
Faculty of Science, University of Ontario Institute of Technology, Oshawa, ON, Canada
[email protected]
Transition metals play a vital role in biology and chemistry. Being the most abundant essential trace
element in the human body, iron participates in crucial physiological processes such as oxygen transport,
electron transfer, and enzymatic catalysis. Zinc is the second most abundant transition metal in human body
after iron. Unlike iron, which is required for certain specific functions, zinc is required for general
metabolism. However, increased dietary iron and zinc may cause Alzheimer’s disease, and is linked to
development of cancer.1 Even though ruthenium is not an essential trace element in the human body, it may
have significant impact on human health; in particular, ruthenium complexes were shown to form cross links with nucleic acids to halt DNA replication. 2 Although significant progress has been made in
monitoring of Fe(II), Fe(III), Zn(II) and Ru(III) as single-analyte ions, as well as in detection of Fe(II)Fe(III) pair, recent research efforts have been focused on the development of assays that allow simultaneous
multi-analyte detection, which is especially important in environmental testings, food chemistry and
molecular biology. 3
We report on development of a thoroughly water soluble platform for rapid and sensitive (ppb to ppm level)
detection of Fe2+, Fe3+, Ru3+, and Zn2+ in multicomponent aqueous solutions. Upon reaction with
abovementioned metal ions, it produces a non-distractive Uv-vis and fluorescence readouts that can be
analyzed and interpreted using logic gates concept. Use of the platform do not require preliminary sample
treatment, resulting in successful metal ions discrimination in situ and thus can be potentially applicable for
analysis of environmental, food, biological and biomedical aqueous systems.
1. (a) C. P. Wen, et al Cancer Res., 2014, 74, 6589-6597; (b) L. C. Costello and R. B. Franklin, Mol.
Cancer, 2006, 5, 17.
2. A. Bergamo, et al. J. Inorg. Biochem., 2012, 106, 90-99
3. Z. Zhang, D.S. Kim, C.-Y. Lin, H. Zhang, A.D. Lammer, V. M. Lynch,I. Popov, O. Š.Miljanić, E. V. Anslyn, J.
L. Sessler, J. Am. Chem. Soc. 2015, 137, 7769-7774.
P41
An Organo-Thulium Family of Single-Ion Magnets: Is Symmetry Enough?
Katie L. M. Harriman, Ilia Korobkov, and Muralee Murugesu*
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada
Single-molecule magnets (SMMs) exhibit slow relaxation of the magnetization of purely molecular origin, making
them excellent candidates for electronics-based applications; specifically in high-density information storage,
molecular spintronics, and quantum computing. However, implementation of these types of materials into practical
devices will rely heavily on increasing their energy barrier to spin reversal (Ueff). Throughout the last decade,
growing research efforts have been directed towards the synthesis of single-ion magnets (SIMs) with the goal of
maximizing Ueff through tailoring single-ion anisotropy. The 4f-elements represent excellent candidates for SIMs
due to their large intrinsic magnetic anisotropy, however, they are often plagued with significant ground state
quantum tunneling of the magnetization (QTM), which drastically reduces Ueff.. This problem becomes even more
difficult to overcome in non-Kramers ions, (integer spin systems) where ground state QTM is not formally forbidden
as it is with Kramers ions (non-integer spin systems). One of the ways to circumvent this problem is to design
systems which exhibit very high symmetry. As such, we have turned our attention towards organometallic
compounds; where we have synthesized a family of cyclooctatetraenide (COT 2-) complexes with thulium, a nonKramers ion (S = 1). Thulium remains one of the most rarely studied lanthanide ions, both in terms of its chemistry
and its slow relaxation properties. This presentation will outline the synthetic route, and the subsequent challenges
faced in designing a family of organo-thulium complexes, as well as their SIM properties investigated through
SQUID magnetometry.
P42
Arsenic Speciation in Mushrooms Subject to Thermal Treatments
Jessica Henry, Iris Koch,* Jennifer Scott,* and Kenneth J. Reimer*
Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON,
Canada
[email protected]; [email protected]; [email protected]; [email protected]
Arsenic is an element found in the environment in many different chemical forms (referred to as species), each
having unique chemical, physical and biological properties. The different species range in their toxicities, with
among the most toxic arsenic species including inorganic forms, such as arsenite (As(III)) and arsenate (As(V)).
Generally, pentavalent organoarsenic compounds are less toxic and aresenobetaine (AB) is the only species
considered non-toxic. Where there are no natural or anthropogenic sources of arsenic contamination, food is the
main source of intake for this metalloid. Higher levels of arsenic are generally found in foods such as seafood, rice,
and sometimes mushroom. AB is the principal arsenic form in seafood and many mushrooms species. Preparations
of food, such as cooking treatments, have been found to alter the arsenic speciation in seafood such as the
degradation of AB to dimethylarsinic acid (DMA), and tetramethylarsonium ion (TETRA), as well as less prevalent
amounts of arsenocholine (AC) and monomethylarsonic acid (MMA). In this study, four edible mushroom species
(Lactarius deliciosus, Leccinum scabrum, Boletus edulis and Calvatia gigantea) were collected and treated to
simulate cooking scenarios (barbequed and fried). The samples were analyzed for total arsenic using ICP-MS and
for arsenic species using HPLC-ICP-MS. A consistent decrease in the total arsenic concentration was seen in all of
the cooked samples, in comparison to their raw (untreated) concentrations. AB was found to be transformed to more
toxic forms in both the fried and barbequed samples for the Calvatia sp.. Therefore, it may be necessary to consider
the effect of thermal treatments on arsenical species when determining risk associated with mushroom intake.
P43
Benzimidazolium Bicarbonates as Air-stable Precursors of N-Heterocyclic
Carbenes (NHCs): Novel Synthetic Routes and Applications to Gold Surfaces
Mina R. Narouz, Christene A. Smith, Cathleen M. Crudden,* and J. Hugh Horton*
Recent results from the Crudden and Horton laboratories demonstrated the formation of ultrastable self-assembled
monolayers (SAMs) of N-heterocyclic carbenes (NHC) on gold surfaces where NHCs were generated in a glove
box using a strong base.1 Although Fèvre et al. showed that imidazol(in)ium bicarbonates could behave as an air
stable source of NHCs, their procedures for the preparation of imidazolium bicarbonates via anion-metathesis
using KHCO3 resulted in highly variable levels of exchange.2 In our current work, novel synthetic routes were
developed to prepare pure, air-stable benzimidazolium bicarbonates ([NHC(H)][HCO3] ) from the iodide
counterparts. For the first time, these bench-stable bicarbonates were shown to effectively form NHC-based SAMs
on gold surfaces in methanol at room temperature without the need for water and oxygen-free conditions.
1
2
Crudden C. M. et al., Nature Chem., 2014, 6, 409-414.
Fèvre M. et al., J. Am.Chem. Soc., 2012, 134, 6776–6784.

48 Inorganic Discussion Weekend 48 Rencontres

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