Kinetic and Mechanistic Studies of Carbenes, Silylenes, and Germylenes

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This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Peter Gaspar, Washington University. This work is focused on studies of short-lived species in carbon, silicon, and germanium chemistry. An understanding of such species, particularly those of silicon and germanium, has important practical implications because they may be important in a number of industrial processes, especially ones in the semiconductor industry. A coordinated set of experiments will be carried out to elucidate chemical reaction mechanisms for short-lived molecules containing divalent carbon, silicon and germanium atoms. A complete understanding of the factors influencing their reactivity will enhance the ability to control their highly useful reactions. Another goal of this project is to determine how the mechanistic ideas of organic chemistry need to be modified to deal with bond-making and bond cleavage below the first-row of the periodic table. This knowledge will extend the usefulness of these ideas in the domain of organometallic chemistry and also enhance their effectiveness in dealing with pure organic chemistry. The rates of reaction of silicon and germanium analogs of important intermediates in organic chemistry will be studied as will the preparation of new types of molecules containing multiple bonds to silicon. The experiments combine the synthesis of new molecules with physical studies of species too short-lived to isolate. Among the latter experiments are the generation of reactive molecules by use of nanosecond pulses of photons from lasers and the monitoring of these short-lived reactions on a time scale of picoseconds to milliseconds.