title: Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds.
abstract: 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 Csp2-Csp3 cross-coupling reactions.
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France).
authors.forename: Vincent
authors.initials: V
authors.lastname: Corcé
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France).
authors.forename: Lise-Marie
authors.initials: LM
authors.lastname: Chamoreau
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France).
authors.forename: Etienne
authors.initials: E
authors.lastname: Derat
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France). jean-philippe.goddard@uha.fr.|Laboratoire de Chimie Organique et Bioorganique EA 4566, Université de Haute-Alsace, Ecole Nationale Supérieure de Chimie de Mulhouse, 3 Bis rue Alfred Werner, 68093 Mulhouse Cedex (France). jean-philippe.goddard@uha.fr.
authors.forename: Jean-Philippe
authors.initials: JP
authors.lastname: Goddard
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France). cyril.ollivier@upmc.fr.
authors.forename: Cyril
authors.initials: C
authors.lastname: Ollivier
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05 (France). louis.fensterbank@upmc.fr.
authors.forename: Louis
authors.initials: L
authors.lastname: Fensterbank
keywords: hypervalent compounds; oxidation; photocatalysis; radicals; silicates