Peroxides of elements other than carbon. Part XVII. The reaction of trialkylstibines and trialkylbismuthines with t-butyl hydroperoxide and with oxygen

Abstract

t-Butyl hydroperoxide reacts with trialkylstibines, R₃M, to give the corresponding stibine oxides, R₃MO, but with trialkylbismuthines to give products such as RO·OBu^t, ROH, and ROR. Both reactions are thought to involve the intermediate metallonium ion R₃MOH, which undergoes nucleophilic attack on H when M = Sb, and on R when M = Bi.

The autoxidation of the stibines and bismuthines involves a radical chain reaction, and gives products similar to those obtained with t-butyl hydroperoxide. It is suggested that an alkylperoxymetallic compound, R₂MO·OR, is formed by homolytic alkylperoxydealkylation at the metal, followed by reduction of the peroxide by R₃M.