Mechanisms of the reactions of three tetrakis(trialkylsilyl)disilenes and a tetraaryldisilene with various haloalkanes such as carbon tetrachloride, chloroform, dichloromethane, which gave the corresponding 1-alkyl-2-chlorodisilanes and/or 1,2-dichlorodisilanes, were investigated in detail. As evidenced by an ESR observation of an intermediate radical, these reactions were quite unusual, forming neutral radical pairs from two closed shell molecules at the first step; no similar reactions have been observed between alkenes and haloalkanes. Low oxidation potentials of these disilenes, large negative activation entropies, and solvent effects for the rates are in good accord with the direct halogen abstraction of disilenes from haloalkanes instead of single-electron transfer at the rate-determining first step. The structure-reactivity relationship of the reactions and the Hammond postulate suggest that the transition state structures for the first step are similar to those for the halogen abstraction by silyl radicals, but more product-like.
ASJC Scopus subject areas
- Colloid and Surface Chemistry