Electrooxidation of Hypercoordinated Derivatives of Silicon and Reactivity of Their Electrogenerated Cation Radicals: 1-Substituted Silatranes.

Electrochemical oxidation of 1-R-substituted silatranes 1 (R = Me, vinyl, (CH 2 ) 2 CN, CH 2 Ph, CH 2 (C 10 H 7 ), Ph, C 6 H 4 Me, p -Cl-C 6 H 4 , Cl)-classical representatives of pentacoordinated silicon compounds-and the formation of their short living cation radicals upon reversible or quasi-reversible one-electron withdrawal were studied by means of cyclic and square-wave voltammetry, faradaic impedance spectroscopy and real-time temperature-dependent EPR spectroelectrochemistry supported by DFT B3PW91/6-311++G(d,p) (C-PCM, acetonitrile) calculations. The main reaction responsible for the decay of 1 +• is shown to be their deprotonation, and ways of increasing the stability of these species are proposed.