硅的高配位衍生物的电氧化及其电生成阳离子自由基的反应性：1-取代硅氮环戊烷。
Electrooxidation of Hypercoordinated Derivatives of Silicon and Reactivity of Their Electrogenerated Cation Radicals: 1-Substituted Silatranes.
作者信息
Romanovs Vitalijs, Belogolova Elena F, Doronina Evgeniya P, Sidorkin Valery F, Jouikov Viatcheslav V
机构信息
Latvian Institute of Organic Synthesis, Aizkraukles 21, LV-1006 Riga, Latvia.
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia.
出版信息
Molecules. 2023 Jul 20;28(14):5561. doi: 10.3390/molecules28145561.
Electrochemical oxidation of 1-R-substituted silatranes (R = Me, vinyl, (CH)CN, CHPh, CH(CH), Ph, CHMe, -Cl-CH, 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 is shown to be their deprotonation, and ways of increasing the stability of these species are proposed.
通过循环伏安法、方波伏安法、法拉第阻抗谱以及由DFT B3PW91/6 - 311++G(d,p)（C - PCM，乙腈）计算支持的实时温度相关EPR光谱电化学，研究了1 - R - 取代硅氮烷（R = 甲基、乙烯基、(CH)CN、苄基、环己基、苯基、对甲苯基、-Cl - CH₂、Cl）——五配位硅化合物的典型代表——的电化学氧化以及在可逆或准可逆单电子夺取时其短寿命阳离子自由基的形成。导致[具体物质]衰变的主要反应被证明是它们的去质子化，并提出了提高这些物种稳定性的方法。
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