GAS-PHASE PHOTOCHEMICAL REACTIONS OF DODECAMETHYLCYCLOHEXASILANE WITH SILICON COMPOUNDS. KINETICS OF SOME INSERTION REACTIONS OF DIMETHYLSILYLENE

Article abstract of DOI:10.1016/S0022-328X(00)83467-1

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.