Group 14 Reactive Intermediates & Organic/Organometallic Photochemistry

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Our NSERC Discovery program focuses on fast kinetics studies of the reactions of divalent and multiply-bonded molecules containing one or more of the heavy tetrel elements (Si, Ge, and Sn), with a view to the development of a comprehensive understanding of their reaction mechanisms and the way they vary with the central element and the electronic and steric characteristics of substituents. Most of the molecules we study are highly reactive, transient species, which we generate using pulsed laser-induced photochemical reactions and detect and monitor directly using fast time-resolved uv-vis spectroscopy. Part of our work involves studying stable molecules containing these functionalities, which can be prepared in advance; their (typically fast) reactions are studied by stopped-flow kinetics, another fast time-resolved spectroscopic method. Our work bridges between the mechanistic behaviour of simply substituted divalent and multiply-bonded derivatives that theory can address with high precision, and the sterically-hindered ones that are of primary interest to synthetic chemists. Molecules of these types hold great potential for applications in synthesis and materials chemistry, and are also relevant to the chemistry of silicon & germanium semiconductor surfaces, for which appropriately substituted derivatives serve as small molecule models. Developing a detailed understanding of the chemistry of these species in various structural situations and under various experimental conditions, and of the mechanisms and scope of the photochemical reactions which produce them, is important for the development of new strategies in synthetic and materials chemistry which are based on the chemistry of these species. Our work serves as a fertile training ground for students in the chemical sciences, who represent the next generation of highly qualified Canadian scientists.