Abstract
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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