title: A Ruthenium(II)-Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation.
abstract: Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of a catalytic system requires regeneration of the Cu(I) active redox state from Cu(II). This is usually achieved using extra reducers that can compete with the Cu(II)(O2) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a Ru(II) photosensitizing subunit with a Cu(II) pre-catalytic moiety assembled within a unique entity is shown to fulfill these requirements. In presence of a sacrificial electron donor and light, electron transfer occurs from the Ru(II) center to Cu(II). In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant (3)O2 activation pathway by the Cu(I) moiety.
authors.affiliation: Laboratoire Chimie et Biologie des Métaux, Université Grenoble-Alpes, CEA, DSV/iRTSV, LCBM-CNRS, UMR5249, 38041 Grenoble (France) http://www-dsv.cea.fr/irtsv/lcbm/bioce.
authors.forename: Wissam
authors.initials: W
authors.lastname: Iali
authors.affiliation: Département de Chimie Moléculaire, Université Grenoble-Alpes; CNRS UMR 5250, BP53, 38041 Grenoble (France).
authors.forename: Pierre-Henri
authors.initials: PH
authors.lastname: Lanoe
authors.affiliation: Laboratoire Chimie et Biologie des Métaux, Université Grenoble-Alpes, CEA, DSV/iRTSV, LCBM-CNRS, UMR5249, 38041 Grenoble (France) http://www-dsv.cea.fr/irtsv/lcbm/bioce. stephane.torelli@cea.fr.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Torelli
authors.affiliation: Département de Chimie Moléculaire, Université Grenoble-Alpes; CNRS UMR 5250, BP53, 38041 Grenoble (France).
authors.forename: Damien
authors.initials: D
authors.lastname: Jouvenot
authors.affiliation: Département de Chimie Moléculaire, Université Grenoble-Alpes; CNRS UMR 5250, BP53, 38041 Grenoble (France).
authors.forename: Frédérique
authors.initials: F
authors.lastname: Loiseau
authors.affiliation: Laboratoire de Reconnaissance Ionique et Chimie de Coordination-Université Grenoble-Alpes, CEA, DSV/iRTSV, LCBM-CNRS, UMR5249, 38041 Grenoble (France).
authors.forename: Colette
authors.initials: C
authors.lastname: Lebrun
authors.affiliation: Laboratoire Chimie et Biologie des Métaux, Université Grenoble-Alpes, CEA, DSV/iRTSV, LCBM-CNRS, UMR5249, 38041 Grenoble (France) http://www-dsv.cea.fr/irtsv/lcbm/bioce. ohamelin@cea.fr.
authors.forename: Olivier
authors.initials: O
authors.lastname: Hamelin
authors.affiliation: Laboratoire Chimie et Biologie des Métaux, Université Grenoble-Alpes, CEA, DSV/iRTSV, LCBM-CNRS, UMR5249, 38041 Grenoble (France) http://www-dsv.cea.fr/irtsv/lcbm/bioce.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Ménage
keywords: copper; dioxygen; oxygenation; photocatalysts; ruthenium