A Ruthenium(II)–Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation |
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| Authors: | Dr. Wissam Iali Dr. Pierre‐Henri Lanoe Dr. Stéphane Torelli Dr. Damien Jouvenot Prof. Frédérique Loiseau Colette Lebrun Dr. Olivier Hamelin Dr. Stéphane Ménage |
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| Affiliation: | 1. 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;2. Département de Chimie Moléculaire, Université Grenoble‐Alpes;3. CNRS UMR 5250, BP53, 38041 Grenoble (France);4. Laboratoire de Reconnaissance Ionique et Chimie de Coordination—Université Grenoble‐Alpes, CEA, DSV/iRTSV, LCBM—CNRS, UMR5249, 38041 Grenoble (France) |
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| 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 CuI active redox state from CuII. This is usually achieved using extra reducers that can compete with the CuII(O2) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a RuII photosensitizing subunit with a CuII 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 RuII center to CuII. In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant 3O2 activation pathway by the CuI moiety. |
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| Keywords: | copper dioxygen oxygenation photocatalysts ruthenium |
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