Electrochemistry of organosilicon compounds and intermediate species containing Si-O and Si=O bonds is considered. Dichloro-, dialkoxy- and dithiosilanes react with electrogenerated superoxide anion to give transient silanones which have been trapped by their insertion into Si-O and Si-H bonds of siloxanes and triorganosilanes; the process thus results in functional siloxane products. The analogous reaction with monochlorosilanes leads to bis-silylperoxides. Peroxodicarbonate anion prepared by cathodic activation of O2 in the presence of CO2 reacts with hydrosilanes yielding, with monohydrosilanes, the derivatives of silylcarboxylic acids whereas with dihydrosilanes corresponding cyclosiloxanes were formed. The mechanisms and kinetics of the considered processes are discussed.
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