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IDW 2002
Friday, October 25th, 2002
19:00-22:00. Registration and Mixer
David Thomson House, McGill University, 3650 McTavish Street.
The scientific sessions will take place in rooms K-500 and M-415 in the Pavillon Principal at the Université de Montréal
Saturday, October 26th, 2002
9:00-10:00. Plenary Lecture:
Professor William D. Jones, Department of Chemistry, University of Rochester, Rochester, NY , USA.
10:30-16:30. Oral Presentations
16:50-18:30. Poster Session
19:30-22:00. Banquet and Poster Presentations Awards
Faculty Club, McGill University, 3450 McTavish Street.
Sunday, October 27th, 2002
9:30-10:50. Oral Presentations
11:10-11:40. Guest Speaker:
Professor D. Scott Bohle, Department of Chemistry, McGill University
11:40-12:10. Closing Remarks and Oral Presentations Awards
Bienvenue à Montréal!
Welcome to Montreal!
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Saturday Morning
9:00-10:00. Room K-500. Plenary Lecture.
Alkane Complexes as Intermediates in C-H Bond Activation Reactions
William D. Jones
Department of Chemistry, University of Rochester, Rochester, NY 14627
10:00-10:30. Coffee Break
Session I (Room K-500)
Session Chair: Annie Michaud
10:30-10:50. K-1. Manganese(II) Dipyrrolides as a Model System for Small Molecule Activation
Patrick Crewdson, Sandro Gambarotta, and Glenn Yap
Department of Chemistry, University of Ottawa
10:50-11:10. K-2. Kinetic and Computer Modeling Studies into the Hydrogenation of Acetophenone by the Novel Hydrido amido Catalyst RuH(NHCMe2CMe2NH2)(PPh3)2
Sean Clapham, Kamaluddin Abdur-Rashid, Alan Lough, and Bob Morris
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
11:10-11:30. K-3. Synthesis and Reactivity of Manganese Complex Derived of Methylcymantrene
Y. Ortin1, N. Lugan1, R. Mathieu1, M. J. McGlinchey2
1 Laboratoire de Chimie de Coordination du CNRS, UPR CNRS 8241, Toulouse, France. 2 Department of Chemistry, McMaster University, Hamilton, Ontario, Canada
11:30-11:50. K-4. Potential Energy Surfaces in Transition States for Associative Reactions of Metal Carbonyl Clusters with P-donor Nucleophiles: Rh4(CO)12
Kevin Bunten, David H. Farrar, and Anthony J. Poë
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
11:50-14:00. Lunch Break
Session II (Room M-415)
Session Chair: John Grey
10:30-10:50. M-1. Anion-dependent structures of noble-metal-complexes of blue-luminescent starburst ligands
Corey Seward, Emily Mitchell, Wenli Jia, and Suning Wang
Department of Chemistry, Queen’s University, Kingston, Ontario
10:50-11:10. M-2. Photoswitching hydrogen-bonded azodibenzoic acid derivatives
Felaniaina Rakotondradany, Tony Whitehead, and Hanadi F. Sleiman.
Department of Chemistry, McGill University, Montreal, Quebec, Canada
11:10-11:30. M-3. Phase Transitions in the Superionic Pb1-xSnxF2 Solid Solution upon Ball-Milling
Georges Dénès , Matthieu Kernec, M. Cecilia Madamba and Marc Poizat
Department of Chemistry and Biochemistry, Laboratory of Solid State Chemistry and Mössbauer Spectroscopy, Laboratories for Inorganic Materials, Concordia University, Montréal, Québec, Canada
11:30-11:50. M-4. Modern Semiempirical SCF MO Methods in Inorganic Chemistry
S. I. Gorelsky1, 2, and A. B. P. Lever2
1 Department of Chemistry, Stanford University, Stanford, California, U.S.A. 2 Department of Chemistry, York University, Toronto, Ontario, Canada
11:50-14:00. Lunch Break
Saturday Afternoon
Session III (Room K-500)
Session Chair: Laurent Groux
14:00-14:20. K-5. Direct Evidence for the Stereochemistry of Transmetalation and Reductive Elimination Processes in Pd-mediated P–C bond formation
Tim J. Brunker,1 Jillian R. Moncarz,2 David S. Glueck,1 Roger D. Sommer,3 and Arnold L. Rheingold3
1 Department of Chemistry, Dartmouth College, Hanover, NH, 03755, USA.
2 Current address: Department of Chemistry, Marietta College, Marietta, OH, 45750, USA. 3 Department of Chemistry, University of Delaware, Newark, DE 19716, USA.
14:20-14:40. K-6. The Palladium Catalyzed Multicomponent Synthesis of Heterocyclic and Amino Acid Based Products
Ragiv Dhawan, and Bruce A. Arndtsen*
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, Canada.
14:40-15:00. K-7. Synthesis and Unusual Skeletal Substitution Chemistry of Aluminatophosphazenes: A Versatile Class of Inorganic Heterocycles
Eric Rivard, Andrew R. McWilliams, Alan J. Lough, and Ian Manners
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
15:00-15:20. K-8. Spectroscopic and Computational Assessment of the Rotational Barrier of a Ferrocenyl-Stabilized Cyclopentadienyl Cation: Evidence for the First Hydroxy-Fulvalene Ligand
Laura E. Harrington,1 Ignacio Vargas-Baca,1 and Michael J. McGlinchey1,2
1 Department of Chemistry, McMaster University, Hamilton, Ontario, Canada. 2 Department of Chemistry, University College Dublin, Dublin, Ireland
15:20-15:50. Coffee Break
Session Chair: Olivier Bourrier
15:50-16:10. K-9. Low valent actinide complexes in molecular activation processes. Synthesis and Reactivity of U(III) and Th(II) polypyrrolides.
Ilia Korobkov, Sandro Gambarotta, Glenn P. Yap
Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada
16:10-16:30. K-10. Me2Al-CH2-PMe2 : A New, Bifunctional Co-Catalyst in the Ni(II)-Catalyzed Oligomerization of PhSiH3
Frédéric-Georges Fontaine, and Davit Zargarian*
Département de Chimie,Université de Montréal, Montréal (Québec), Canada H3C 3J7
16:30-16:50. Poster Synopses
16:50-18:30. Poster Session
Session IV (Room M-415)
Session Chair: Rémi Beaulac
14:00-14:20. M-5. Metal-Metal Coupling in Asymmetric Dinuclear Mixed-Valence Ruthenium Complexes
Joseph Kahenya and Robert.J.Crutchley*
Ottawa-Carleton Chemistry Institute, Department of Chemistry, Carleton University, Ottawa, Ontario, Canada
14:20-14:40. M-6. Anticeramic Yield: Ceramic Precursors in Polymer-Assisted Vapour Deposition versus Classical Polymeric Route
Sanela Martic*, Nathalie Camire**, Eric Gagnon*, Abdelatif Jaouad**, Cetin Aktik** and Mihai Scarlete*
* Bishop's University, Lennoxville, Quebec, Canada, **Universite de Sherbrooke, Sherbrooke, Quebec, Canada
14:40-15:00. M-7. Tuning the Luminescence and Electroluminescence of Diphenylboron Complexes of Substituted 2-(2'-Pyridyl)indoles
Qinde Liu1, Maria S. Mudadu2, Randolph Thummel2, Ye Tao3, and Suning Wang1
1 Department of Chemistry, Queen’s University, Kingston, Ontario, K7L 3N6, Canada. 2 Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA
3 Institute for Microstructural Sciences, National Research Council, 100 Sussex Drive, Ottawa, K1A 0R6, Canada
15:00-15:20. M-8. Scavenging with TEMPO to Identify Peptide- and Protein-based Radicals by Mass Spectrometry: Advantages of Spin Scavenging over Spin Trapping
P. John Wright and Ann M. English*
Department of Chemistry and Biochemistry, Concordia University, 1455 de Maisonneuve Boulevard West, Montreal, Quebec, Canada
15:20-15:50. Coffee Break
Session Chair: François Baril-Robert
15:50-16:10. M-9. Synthesis and Characterization of Phosphido-Coated Gold Nanoclusters
Diana M. Stefanescu, and David S. Glueck*
Department of Chemistry, Dartmouth College, Hanover, NH, USA
16:10-16:30. M-10. Optical Properties of Er3+-Doped Nanocrystalline Gd2O3
Fiorenzo Vetrone1, John-Christopher Boyer1, John A. Capobianco1, Adolfo Speghini2 and Marco Bettinelli2
1 Department of Chemistry and Biochemistry, Concordia University, 1455 de Maisonneuve Blvd. W., Montreal, Quebec, Canada, H3G 1M8. 2 Dipartimento Scientifico e Tecnologico, Università di Verona, and INSTM, UdR Verona, Ca' Vignal, Strada Le Grazie 15, I-37134 Verona, Italy
16:30-16:50. Poster Synopses
16:50-18:30. Poster Session
19:30-22:30. Banquet
Sunday Morning
Session V (Room K-500)
Session Chair: Ragiv Dhawan
9:30-9:50. K-11. A Three-Coordinate Iron Hydride Complex as a Model for Reactive Intermediates of the Enzyme Nitrogenase
Jeremy M. Smith, Rene J. Lachicotte, and Patrick L. Holland
Department of Chemistry, University of Rochester, Rochester, NY, USA
9:50-10:10. K-12. Solid State Structures of Oligonuclear Ruthenium Light Harvesting Arrays
Matthew Polson2, John Lotoski1, Olof Johansson1 Nicholas Taylor1, and Garry Hanan2
1 Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada. 2 Département de Chimie, Université de Montréal, Montréal, Quebec, Canada
10:10-10:30. K-13. Synthesis and Application in Catalysis of New Versatile Dendritic Architectures Built Using a Simple Divergent Methodology
Olivier Bourrier and Ashok K. Kakkar.
Department of Chemistry, McGill University, Montreal, QC, Canada
10:50-11:10. Coffee Break
Session II (Room M-415)
Session Chair: Adam Dickie
9:30-9:50. M-11. The Synthesis, Characterization, and Bioconjugation of Tc/Re Metallocarboranes
O.O. Sogbein, P.Morel, and J.F. Valliant
Department of Chemistry, McMaster University, Hamilton, Ontario, Canada
9:50-10:10. M-12. Kinetics and Mechanisms of Abiotic Methylation of Aqueous Mercury
Valbona Celo and Susannah Scott
Department of Chemistry, University of Ottawa, Ottawa, Canada
10:10-10:30. M-13. S-Nitrosation of Recombinant Calbindin D28K From Human Brain Mediated by Cu,Zn Superoxide Dismutase
Limei Tao and Ann English*
Department of Chemistry and Biochemistry, Concordia University, 1455, de Maisonneuve Blvd. W., Montreal, Quebec, Canada
10:30-10:50. M-14. The Doubly Disordered Ba1-xSnxCl1+yF1-y Solid Solution: The First Example of a Mixture of Sn2+ Stannous Ions and Covalently Bonded tin(II) in the Same Material
Georges Dénès and Abdualhafeed Muntasar
Department of Chemistry and Biochemistry, Laboratory of Solid State Chemistry and Mössbauer Spectroscopy, Laboratories for Inorganic Materials, Concordia University, Montréal, Québec, Canada
10:50-11:10. Coffee Break
Closing Session (Room K-500)
Session Chair: Hassan S. Bazzi
11:10-11:40. K-14. Chemical Biology of Nitric Oxide and its Electrophilic Addition Products: New Access to ONNO Frameworks
Navamoney Arulsamy1, D. Scott Bohle2, and Jerome Imonigie1
1 Department of Chemistry, University of Wyoming, Laramie, Wyoming, USA. 2 Department of Chemistry, McGill University, Montreal, Quebec, Canada
11:40-12:10. Closing Remarks and Presentations Awards
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ABSTRACTS OF ORAL PRESENTATIONS
K= Room K-500, M= Room M-415
Plenary Lecture:
Alkane Complexes as Intermediates in C-H Bond Activation Reactions
William D. Jones
Department of Chemistry, University of Rochester, Rochester, NY 14627
A series of alkyl hydride complexes have been studied of the type Tp'Rh(L)(R)(H) where L=neopentylisocyanide and R=Me, Et, n-Pr, n-Bu, i-Pr and s-Bu. The secondary alkyl complexes are found to rearrange to primary alkyl complexes prior to elimination of alkane. Stereochemical probes are used to investigate the reversibility of the C-H bond-forming/bond-cleavage steps of the reactions. Deuterium labeling is used to monitor the rearrangements, and the isotope effect for reductive bond formation is determined. Activation of the C-H/C-D bonds in CH2D2 is examined to probe the kinetic selectivity for oxidative bond cleavage. These results are combined to give an overall picture of the energetics of C-H bond activation in which the (commonly observed ) inverse equilibrium isotope effect arises as a result to two opposing normal kinetic isotope effects. A summary of the relative rates of oxidative bond cleavage, migration, and alkane dissociation will be presented and compared with other observations in the literature. Relative rates of activation of several alkane C-H bonds will be compared. In addition, new results on the relative coordination ability of different types of C-H bonds will be presented.
K-1. Manganese(II) Dipyrrolides as a Model System for Small Molecule Activation
Patrick Crewdson, Sandro Gambarotta, and Glenn Yap
Department of Chemistry, University of Ottawa
An exciting field of study which is currently being undertaken in the literature is that of the photo-oxidation of water. This process, which is mediated by a poorly known manganese (II) tetrameric μ-oxo bridged complex, as well as a complex protein structure, could conceivably lead to a cheap and abundant fuel source. To this end we have endeavored to explore the synthesis of manganese clusters in order to model the behaviour of the tetramer core of the active enzyme. Manganese (II) alkyls were successfully made as precursors for assembling cluster structures. Though manganese alkyls are not unknown in the literature there are very few reported syntheses. We were able to synthesize several novel and readily available Manganese (II) alkyls. By combining the Manganese dialkyls with dipyrrolide ligands several dimeric and octameric clusters were prepared. Crystal structures and magnetic properties, as well as preliminary insights into their chemical behaviour will be discussed.
K-2. Kinetic and Computer Modeling Studies into the Hydrogenation of Acetophenone by the Novel Hydrido-amido Catalyst RuH(NHCMe2CMe2NH2)(PPh3)2
Sean Clapham, Kamaluddin Abdur-Rashid, Alan Lough, and Bob Morris
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
The first amino-amido hydride complex RuH(NHCMe2CMe2NH2)(PPh3)2 (1) has been structurally characterized. The kinetic studies of the hydrogenation of acetophenone catalyzed by 1 in C6D6 under hydrogen gas are presented. A computer model of the mechanism of hydrogenation is discussed. Both kinetics and model show that the addition of dihydrogen to the Ru=N bond is the rate determining step. The formate compound RuH(HCOO)(tmen)(PPh3)2 models the transition state for the hydrogenation of the ketone. 1 reacts with several weakly acidic reagents.
K-3. Synthesis and Reactivity of Manganese Complex Derived of Methylcymantrene
Y. Ortin1, N. Lugan1, R. Mathieu1, M. J. McGlinchey2
1 Laboratoire de Chimie de Coordination du CNRS, UPR CNRS 8241, Toulouse, France
2 Department of Chemistry, McMaster University, Hamilton, Ontario, Canada
Non-heteroatom substituted carbene complexes play a key role both as reagents and as catalysts in organic synthesis: cyclopropanation of alkenes, ring-opening metathesis polymerization (ROMP), or ring-closing metathesis (RCM), etc. In this context, the reactivity of new non-heteroatom substituted carbene complexes of manganese, and particularly propynylidene complexes of the type MeCp(CO)2Mn=C(R')C≡CR", was investigated. The first part of this work deals with the protocol set up to prepare non-substituted-carbene complexes of manganese in particular manganese propynylidene complexes. In second part, we present the dynamic behaviour of polynuclear complexes resulting from the coordination of additional [Co2(CO)6] or [MeCp(CO)2Mn] fragments to the alkyne moiety of the manganese propynylidene complexes. This study allowed us to observe unprecedented fluxional processes: on the one hand, dynamic equilibration of eta1-carbene and eta2-alkyne moieties and on the other hand, rapid migration of the carbene fragment over the three carbonyl ligands.
1. Y. Ortin, Y. Coppel, N. Lugan, R. Mathieu, M. J. McGlinchey J. C. S., Chem. Comm. (2001), 1690-1691.2. Y. Ortin, Y. Coppel, N. Lugan, R. Mathieu, M. J. McGlinchey J. C. S., Chem. Comm. (2001), 2636-2637.
K-4. Potential Energy Surfaces in Transition States for Associative Reactions of Metal Carbonyl Clusters with P-donor Nucleophiles: Rh4(CO)12
Kevin Bunten, David H. Farrar, and Anthony J. Poë
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
The metal carbonyl cluster Rh4(CO)12 reacts with a wide variety of P-donor nucleophiles solely by an associative mechanism, and the rate constants can be analyzed quantitatively according to the electronic and steric properties of the nucleophiles. It is clearly necessary to include what has become known as the "Aryl Effect" in these analyses, together with positive contributions to the rates of p-acidity effects due to phosphite nucleophiles. These results provide the basis for general method of assessing the ways in which such results can provide a rationale for methods of tuning catalysts for optimum performance.
K-5. Direct Evidence for the Stereochemistry of Transmetalation and Reductive Elimination Processes in Pd-mediated P–C bond formation
Tim J. Brunker,1 Jillian R. Moncarz,2 David S. Glueck,1 Roger D. Sommer,3 and Arnold L. Rheingold3
1 Department of Chemistry, Dartmouth College, Hanover, NH, 03755, USA.