Carbene chemistry. Part VIII. The thermal decomposition of trichloromethyltrifluorosilane: a kinetic investigation

Abstract

The gas-phase thermal decomposition of trichloromethyltrifluorosilane (CCl₃·SiF₃) at 100–160 °C and 10–100 Torr initial pressure in the presence of alkenes (2,3-dimethylbut-2-ene, cis-, or trans-but-2-ene) is first order in silane; the rate constant is independent of the olefin used and the surface to volume ratio and is given by (i). log₁₀(k/s^–1)= 12.794 ± 0.110 –(126.0 ± 2.6) kJ mol^–1/2.303RT(i) These results provide strong evidence for the participation of free dichlorocarbene in these reactions.