Silicates as Latent Alkyl Radical Precursors: Visible‐Light Photocatalytic Oxidation of Hypervalent Bis‐Catecholato Silicon Compounds

This works introduces hypervalent bis‐catecholato silicon compounds as versatile sources of alkyl radicals upon visible‐light photocatalysis. Using Ir[(dF(CF 3 )ppy) 2 (bpy)](PF 6 ) (dF(CF 3 )ppy=2‐(2,4‐difluorophenyl)‐5‐trifluoromethylpyridine, bpy=bipyridine) as catalytic photooxidant, a series of alkyl radicals, including highly reactive primary ones can be generated and engaged in various intermolecular homolytic reactions. Based on cyclic voltammetry, Stern–Volmer studies, and supported by calculations, a mechanism involving a single‐electron transfer from the silicate to the photoactivated iridium complex has been proposed. This oxidative photocatalyzed process can be efficiently merged with nickel‐catalyzed C   sp   2C   sp   3cross‐coupling reactions.