期刊
MOLECULES
卷 28, 期 14, 页码 -出版社
MDPI
DOI: 10.3390/molecules28145561
关键词
silatranes; cation radicals; hypercoordination; electrochemistry; EPR spectroscopy
The electrochemical oxidation of 1-R-substituted silatranes 1, classical representatives of pentacoordinated silicon compounds, and the formation of their short living cation radicals were studied. The main reaction responsible for the decay of these cation radicals is deprotonation, and strategies to increase their stability are proposed. The study involved various techniques such as cyclic and square-wave voltammetry, faradaic impedance spectroscopy, real-time temperature-dependent EPR spectroelectrochemistry, and DFT calculations.
Electrochemical oxidation of 1-R-substituted silatranes 1 (R = Me, vinyl, (CH2)(2)CN, CH2Ph, CH2(C10H7), Ph, C6H4Me, p-Cl-C6H4, 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(+& BULL;) is shown to be their deprotonation, and ways of increasing the stability of these species are proposed.
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