Nowadays, the quest of new radical precursors based on heteroatom complexes occupies an increasingly prominent position in contemporary research. Herein, we investigated the behavior and the limitations of hexa‐ or pentacoordinated organochlorosilanes and related pentacoordinated silyliums as new families of complexes for the generation of radicals under photocatalytic reductive conditions. Particularly, treatment of chlorophenylbis[N,S‐pyridine‐2‐thiolato(−)]silicon(IV) or the related silylium derivative with the fac‐Ir(ppy)₃ (5 mol‐%)/NEt₃ (1.5 equiv.) system under blue LEDs irradiation generates a thiopyridyl radical which can participate in the formation of a carbon−sulfur bond by reaction with an allylsulfone. Computational studies supported this experimental finding, and particularly by showing that homolytic fragmentation of C−Ts bond is favored over the fragmentation of thiopyridyl radical.

中文翻译：

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迈向超配位硅物种的可见光光催化还原

如今，对基于杂原子配合物的自由基自由基的探索在当代研究中占有越来越重要的地位。在本文中，我们研究了六配位或五配位有机氯硅烷和相关的五配位硅烷基的行为及其局限性，这些新配位族是在光催化还原条件下生成自由基的新配合物。特别是用fac -Ir（ppy）₃（5 mol％）/ NEt ₃处理氯苯基双[N，S-吡啶-2-硫代（-）]硅（IV）或相关的甲硅烷基衍生物（1.5当量）系统在蓝色LED照射下会生成一个硫代吡啶基，该基团可以通过与烯丙基砜反应来参与碳硫键的形成。计算研究支持了这一实验发现，特别是通过显示C-Ts键的均质裂解比硫代吡啶基自由基的裂解更受青睐。