期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 39, 页码 11414-11418出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201504963
关键词
hypervalent compounds; oxidation; photocatalysis; radicals; silicates
资金
- UPMC
- UHA
- CNRS
- IUF
- ANR NHCX [11-BS07-008]
- COST Action [CM1201]
This works introduces hypervalent bis-catecholato silicon compounds as versatile sources of alkyl radicals upon visible-light photocatalysis. Using Ir[(dF(CF3)ppy)(2)(bpy)]-(PF6) (dF(CF3)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-sp2-C-sp3 cross-coupling reactions.
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