Abstract
The free radical γ-radiation induced reactions in solutions of trichloroethylene in triethylsilane were investigated at 65° C. The main products, formed by a chain mechanism are cis- and trans-dichloroethylene, triethylchlorosilane, dichlorovinyltriethylsilane (Et 3SiCHCCl 2) and hydrogen chloride. The results are interpreted in terms of a mechanism in which Et 3SiCl is formed by direct chlorine abstraction from C 2Cl 3H by the Et 3Si • radical. Et 3SiCHCCl 2 is formed via a two step mechanism addition of an Et 3Si • radical to C 2Cl 3H being followed by unimolecular chlorine elimination. Product distribution in the Et 3SiH/C 2Cl 3H system and in competitive experiments in the presence of chloroform and 1-bromopentane was used for the estimation of relevant rate constants ratios.
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