Reactions of Trifluoromethyl Radicals with Monosilane and Monosilane-d4

Abstract

Arrhenius parameters for the reactions of trifluoromethyl radicals, produced by the photolysis of hexafluoroazomethane, with SiH4 and SiD4 have been measured. It has been found that CF3 radicals are more reactive than CH3, the difference in reactivity being due to lower activation energies, as the A factors are almost identical. A theoretical value of E a obtained by the BEBO method using a simple three‐mass‐point model is compared with the experimental. The BEBO and LEPS methods have been used to predict kinetic isotope effects with and without tunneling corrections for comparison with experimental results.