Abstract
AbstractNowadays, 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.
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