Recent Developments in Organosilicon Electrochemistry

摘要

Electrochemistry of organic derivatives of silicon started more than 30 years ago with the reductive cleavage of Si-Cl bonds. Since then, silyl anions - primary intermediates of this process, - were extensively exploited to form disilanes and polysilanes. Recently it was shown that electrochemical activation of Si-Cl bonds under special conditions offers the opportunity to generate not only R_3Si~--species but a large palette of specific and highly reactive silicon intermediates as well such as silanones and silyl radicals. Electrogeneration of transient silanones prepared in situ from the basic starting material - chloro, alkoxy and alkylthiosilanes - allow functionalization of commercial siloxanes and polysiloxanes by inserting a new XYSiO fragment carrying various organic functional groups (X,Y) into the backbone of the target siloxane. Silyl radicals, electrochemically produced by different ways, make possible direct silylation of unsaturated compounds. Electrochemical behavior of stable disilenes, digermenes, silatranes and silylium-type species has also been studied.