Premium
Silicates as Latent Alkyl Radical Precursors: Visible‐Light Photocatalytic Oxidation of Hypervalent Bis‐Catecholato Silicon Compounds
Author(s) -
Corcé Vincent,
Chamoreau LiseMarie,
Derat Etienne,
Goddard JeanPhilippe,
Ollivier Cyril,
Fensterbank Louis
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504963
Subject(s) - chemistry , hypervalent molecule , photochemistry , photocatalysis , radical , alkyl , iridium , catalysis , visible spectrum , electron transfer , organic chemistry , materials science , optoelectronics , reagent
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.