Journal of Organometallic Chemistry p. 149 - 158 (1981)
Update date:2022-08-17
Topics:
Davidson, Iain M.T.
Ostah, Naaman A.
Attempts to measure the kinetics of gas-phase insertion reactions of dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, are described.Insertion of dimethylsilylene into silicon-hydrogen bonds was the main reaction with trimethylsilane, pentamethyldisilane, and sym-tetramethyldisilane; in all cases the activation energy for insertion was zero, and the rate constants were in the ratio of 1:3.1:4.3.Dimethylsilylene also inserted cleanly into hydrogen chloride with an activation energy of 28 kJ mol-1.Photochemical reactions with methylchlorosilanes were much more complex, involving little or no silylene chemistry; such reactions as did occur appeared to proceed almost entirely by radical mechanisms.
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