Dedicated to Philippe Renaud in celebration of his 60th birthday and with all our friendship 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 hexaor 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(À )]silicon(IV) or the related silylium derivative with the fac-Ir(ppy) 3 (5 mol-%)/NEt 3 (1.5 equiv.) system under blue LEDs irradiation generates a thiopyridyl radical which can participate in the formation of a carbonÀ sulfur bond by reaction with an allylsulfone. Computational studies supported this experimental finding, and particularly by showing that homolytic fragmentation of CÀ Ts bond is favored over the fragmentation of thiopyridyl radical. Scheme 7. Proposed mechanism for the formation of 6. Scheme 8. Photocatalytic reaction using phenyl[tris(phenylsulfanyl)]silane as a radical precursor.Scheme 9. Synthesis of hexacoordinated silicon compounds 5b and 5c, using N,S-pyridine-2-thiolato ligand followed by their reactivity in the presence of allylsulfone 2 under visible-light photoreductive conditions. Formation of allylsulfide 6.