Formation of silylenes in the thermolysis of methylchlorodisilanes

Abstract

The kinetics of the following silylene eliminations in the gas phase have been measured: Me₃SiSiMe₂Cl → Me₂Si + Me₃SiCl, log₁₀k/s^–1=(11.69 ± 0.33)–(209.7 ± 4.5) kJ mol^–1/2.303 RT, Cl₂MeSiSiMe₂Cl → MeSiCl + Me₂SiCl₂, log₁₀k/s^–1=(12.45 ± 0.76)–(195.6 ± 10.0) kJ mol^–1/2.303 RT, Cl₂MeSiSiMeCl₂→ MeSiCl + MeSiCl₃, log₁₀k/s^–1=(12.06 ± 0.35)–(192.4 ± 4.6) kJ mol^–1/2.303 RT. The significance of these Arrhenius parameters is discussed. Some insertion reactions of dimethylsilylene and methylsilylene are described.