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Efficient Ruthenium Nanocatalysts in Liquid–Liquid Biphasic Hydrogenation Catalysis: Towards a Supramolecular Control through a Sulfonated Diphosphine–Cyclodextrin Smart Combination

Authors

  • Dr. Miguel Guerrero,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205, Route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse (France)
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  • Dr. Yannick Coppel,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205, Route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse (France)
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  • Dr. Nguyet Tran Thanh Chau,

    1. Ecole Normale Supérieure de Chimie de Rennes, CNRS, UMR6226, Avenue du Général Leclerc, CS 50837, F-35708 Rennes cedex 7 (France)
    2. Université européenne de Bretagne
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  • Prof. Alain Roucoux,

    1. Ecole Normale Supérieure de Chimie de Rennes, CNRS, UMR6226, Avenue du Général Leclerc, CS 50837, F-35708 Rennes cedex 7 (France)
    2. Université européenne de Bretagne
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  • Dr. Audrey Denicourt-Nowicki,

    1. Ecole Normale Supérieure de Chimie de Rennes, CNRS, UMR6226, Avenue du Général Leclerc, CS 50837, F-35708 Rennes cedex 7 (France)
    2. Université européenne de Bretagne
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  • Prof. Eric Monflier,

    1. UMR CNRS 8181, Université d'Artois, Faculté des Sciences Jean Perrin, Rue Jean Souvraz, SP 18 - F-62307 Lens Cedex (France)
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  • Dr. Hervé Bricout,

    1. UMR CNRS 8181, Université d'Artois, Faculté des Sciences Jean Perrin, Rue Jean Souvraz, SP 18 - F-62307 Lens Cedex (France)
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  • Dr. Pierre Lecante,

    1. CNRS, Centre d'Elaboration de Matériaux et d'Etudes Structurales (CEMES), 29, rue Jeanne Marvig, BP 4347, 31055 Toulouse Cedex (France)
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  • Dr. Karine Philippot

    Corresponding author
    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205, Route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT; LCC, F-31077 Toulouse (France)
    • CNRS, LCC (Laboratoire de Chimie de Coordination), 205, Route de Narbonne, F-31077 Toulouse (France), Fax: (+33) 561553003

    Search for more papers by this author

Abstract

The combination between a sulfonated diphosphine (L) and a cyclodextrin (CD) allowed the preparation of very stable water-soluble ruthenium nanoparticles (RuNPs) that displayed pertinent catalytic performances in hydrogenation of unsaturated substrates with a supramolecular control effect of the cyclodextrin. For comparison purpose, the RuNPs were produced by hydrogenation of the organometallic [Ru(1,5-cyclooctadiene)(1,3,5-cyclooctatriene)] complex under mild conditions (3 bar H2; room temperature) and in the presence of L or a L/CD mixture as stabilizer leading to Ru/L and Ru/L/CD systems, respectively. The so-obtained nanoparticles were fully characterized by complementary techniques. Interestingly, NMR investigations evidenced 1) the strong coordination of the sulfonated diphosphine ligand at the metallic surface and 2) in the presence of cyclodextrin, the formation of an inclusion complex between L and CD that modified the coordination mode of the diphosphine. The investigation of both RuNPs systems in biphasic hydrogenation of unsaturated substrates pointed out relevant differences in terms of reactivity, thus evidencing the influence of the supramolecular interaction at the metallic surface on the catalytic performances of the nanocatalysts. This work took advantage of the supramolecular properties of a cyclodextrin to modulate the surface reactivity of diphosphine-stabilized ruthenium nanoparticles and may open new opportunities in the field of nanocatalysis.

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