Leigh, Willie - McMaster University - Department of Chemistry & Chemical Biology

研究领域

The group's research interests are in the general areas of physical-organic and physical-organometallic chemistry, and mechanistic organic and organometallic photochemistry. Our work focuses largely on mechanistic studies of the reactions of highly reactive molecules and reaction intermediates in organosilicon, -germanium, and -tin chemistry, using fast time-resolved spectroscopic methods to enable their direct detection and detailed studies of their reactivities. Students gain experience in a wide variety of synthetic, photochemical, analytical, and spectroscopic techniques. These include the common ones - such as high field NMR spectroscopy, FT-IR spectroscopy, GC and HPLC, GC/MS, and single crystal x-ray crystallography - as well as specialized techniques such as laser flash photolysis (LFP) and stopped-flow kinetics (SFK) methods. The LFP technique allows the study of intrinsically short-lived (50 ns to ~100 ms) reactive molecules in solution, which are generated by photochemical reactions. The SFK method allows the study of fast reactions of isolable but nevertheless highly reactive molecules on timescales of ~10 ms to minutes. Both methods enable the measurement of the uv-vis absorption spectra, lifetimes, and rate constants for their reactions with various added substrates, and of the intermediates that are formed during the course of these reactions. Fast kinetic studies by LFP are supported with preparative photochemical experiments to enable the isolation and identification of the ultimate products of the reactions of interest.

近期论文

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S. S. Kostina, T. Singh, and W. J. Leigh*, "Electronic and Steric Effects on the Lewis Acidities of Transient Silylenes and Germylenes – Equilibrium Constants for Complexation with Chalcogen and Pnictogen Donors.", Organometallics, 31, 3755-3767. | Get Reprint | Supporting Information S. S. Kostina, T. Singh, and W. J. Leigh*, "Kinetics and Mechanisms of the Reactions of Transient Silylenes with Amines", J. Phys. Org. Chem., 24, 937-946. | Get Reprint | Supporting Information P. S. Billone, K. Beleznay, C. R. Harrington, L. A. Huck, and W. J. Leigh*, "A Glimpse at the Chemistry of GeH2 in Solution. Direct Detection of an Intramolecular Germylene-Alkene π-Complex", J. Am. Chem. Soc., 133, 10523-10534 (2011) . | Get Reprint | Supporting Information S. S. Kostina and W. J. Leigh*, "Silanones and Silanethiones from the Reactions of Transient Silylenes with Oxiranes and Thiiranes in Solution. The Direct Detection of Diphenylsilanethione", J. Am. Chem. Soc., 133, 4377-4388 (2011). | Get Reprint | Supporting Information L. A. Huck and W. J. Leigh*, "Kinetic and Mechanistic Studies of the Reactions of Diarylgermylenes and Tetraaryldigermenes with Carbon Tetrachloride", Can. J. Chem., 89, 241-255 (2011). | Get Reprint| | Supporting Information M. Bancerz, L. A. Huck, W. J. Leigh, G. Mladenova, K. Najafian, X. Zeng, and E. Lee-Ruff,* "Photochemical Generation of Thiophene Analogs of 9-Fluorenyl Cation", J. Phys. Org. Chem., 23, 1202-1213 (2010). (DOI 10.1002/poc.1754) W. J. Leigh*, S. S. Kostina, A. Bhattacharya, and A. G. Moiseev, "A Fast Kinetics Study of the Reactions of Transient Silylenes with Alcohols. Direct Detection of Silylene-Alcohol Complexes in Solution", Organometallics, 29, 662-670 (2010). |Get Reprint | Supporting Information L. A. Huck and W. J. Leigh*, "A Better Sunscreen – Conformational Effects on Spectral Properties", J. Chem. Ed., 87, 1384 (2010). | Get Reprint L. A. Huck and W. J. Leigh*, "Kinetic and Mechanistic Studies of the Formal (1+2)- and (1+4)-Cycloadditions of Germylenes to Conjugated Dienes." Organometallics, 28, 6777-6788 (2009). |Get Reprint | Supporting Information A. G. Moiseev, E. Coulais, and W. J. Leigh*, "The Photochemistry of Cyclic Trisilanes. “Spring-Loaded” Precursors to Methylphenylsilylene." Chem. Eur. J. 15, 8485-8491 2009. |Get Reprint | Supporting Information F. Lollmahomed and W. J. Leigh*, “Laser Flash Photolysis Studies of Some Dimethylgermylene Precursors”, Organometallics, 28, 3239-3246 (2009). [Get Reprint | Supporting Information] L. A. Huck, G. D. Potter, H. A. Jenkins, J. F. Britten, and W. J. Leigh,* "1,1-Bis[4-(trifluoromethyl)phenyl]germetane", Acta Cryst. E65, m602. [Get Reprint] F. Lollmahomed, W. J. Leigh*, L. A. Huck, S. S. Chitnis, and C. R. Harrington, “Time-Resolved Spectroscopic Studies of the Reactivities of Transient Germylenes in Methanol and Tetrahydrofuran Solution”, Organometallics 28, 1484-1494 (2009). [Get Reprint | Supporting Information] A. Moretto, M. Crisma, F. Formaggio, L. A. Huck, D. Mangion, W. J. Leigh, and C. Toniolo*, “Photoinduced Intramolecular Macrocyclization Reaction between a Bpa and a Met Residue in a Helical Peptide: 3D-Structures of the Diastereomeric Products Formed”, Chem. Eur. J. 15, 67-70 (2009). [Get Reprint | Supporting Information] A. Chrostowska*, V. Lemierre, A. Dargelos, P. Bayl�re, W. J. Leigh, G. Rima, L. Weber, and M. Schimmel, “Gas-Phase Synthesis and Characterization of Heteroleptic Divalent Germanium Compounds by FVT/UV-PES”, J. Organomet. Chem. 694, 43-51 (2009). [Get Reprint] W. J. Leigh*, A. G. Moiseev, E. Coulais, F. Lollmahomed, and M. S. Askari, “Substituent Effects on Silene Reactivity. Reactive Silenes from Photolysis of Phenylated Tri- and Tetrasilanes”, Can. J. Chem. 86, 1105-1117 (2008). [Get Reprint | Supporting Information] W.J. Leigh,* G.D. Potter, L.A. Huck, and A. Bhattacharya, “Competing Germene and Germylene Extrusion from Photolysis of 1,1-Diarylgermacyclobutanes. Substituent Effects on Germene Reactivity”, Organometallics 27, 5948-5959 (2008). [Get Reprint | Supporting Information] A. Moretto, M. Crisma, F. Formaggio, L. A. Huck, D. Mangion, W. J. Leigh, and C. Toniolo, “Photoinduced Intramolecular Macrocyclizations on Helical Bpa/Met Oligopeptides", Peptides 2008: Chemistry of Peptides in Life Science, Technology and Medicine (Proceedings of the 30th European Peptide Symposium, Helsinki, 2008). [Get Reprint] A.G. Moiseev and W.J. Leigh,* "A Comparison of the Reactivities of Dimethylsilylene (SiMe2) and Diphenylsilylene (SiPh2) in Solution by Laser Flash Photolysis Methods", Organometallics 26, 6277-6289 (2007). [Get Reprint | Supporting Information] A.G. Moiseev and W.J. Leigh,* "The Direct Detection of Diphenylsilylene and Tetraphenyldisilene in Solution", Organometallics 26, 6268-6276 (2007). [Get Reprint | Supporting Information]