Mechanism of oxidation of organopolysilanes by peroxy acids

Abstract

To determine the regularities in the energy change of the highest occupied molecular orbital of a polysilane, which is localized in the Si-Si bond, the authors investigate the formation of charge-transfer complexes of tetracyanoethylene with some peralkylated and chlorosubstituted polysilanes. In oxidation of organopolysilanes by peroxybenzoic acid, the reaction is retarded with increasing values of I/sub 1/ /SUP D/ in the range of individually taken series of permethylated or chloro-substituted polysilanes. Replacement of an alkyl group at Si by a C1 atom leads to acceleration of the reaction, despite an increase of I/sub 1/ /SUP D/ .