Carbohydrate-Derived 1,3-Diphosphite Ligands as Chiral Nanoparticle Stabilizers: Promising Catalytic Systems for Asymmetric Hydrogenation

Authors

  • Aitor Gual Dr.,

    1. Department de Química Física I Inorgànica, Universitat Rovira I Virigli, Marcel⋅li Domingo, s/n, 43007 Tarragona (Spain), Fax: (+34) 977-559563
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  • Cyril Godard Dr.,

    1. Department de Química Física I Inorgànica, Universitat Rovira I Virigli, Marcel⋅li Domingo, s/n, 43007 Tarragona (Spain), Fax: (+34) 977-559563
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  • Karine Philippot Dr.,

    1. CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, LCC, 205 route de Narbonne, 31077 Toulouse (France), Fax: (+33) 561553003
    2. Université Paul Sabatier, INPT, 118 route de Narbonne, 31077 Toulouse (France)
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  • Bruno Chaudret Prof.,

    1. CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, LCC, 205 route de Narbonne, 31077 Toulouse (France), Fax: (+33) 561553003
    2. Université Paul Sabatier, INPT, 118 route de Narbonne, 31077 Toulouse (France)
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  • Audrey Denicourt-Nowicki Dr.,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 0223238199
    2. Université Européenne de Bretagne, 5 bd. Laënnec, 35000 Rennes (France)
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  • Alain Roucoux Prof.,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 0223238199
    2. Université Européenne de Bretagne, 5 bd. Laënnec, 35000 Rennes (France)
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  • Sergio Castillón Prof.,

    1. Department de Química Analítica I Orgànica, Universitat Rovira I Virigli, Marcel⋅li Domingo, s/n, 43007 Tarragona (Spain)
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  • Carmen Claver Prof.

    1. Department de Química Física I Inorgànica, Universitat Rovira I Virigli, Marcel⋅li Domingo, s/n, 43007 Tarragona (Spain), Fax: (+34) 977-559563
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Abstract

Metallic Ru, Rh, and Ir nanoparticles were prepared by the decomposition of organometallic precursors under H2 pressure in the presence of 1,3-diphosphite ligands, derived from carbohydrates, as stabilizing agents. Structural modifications to the diphosphite backbone were found to influence the nanoparticles′ size, dispersion, and catalytic activity. In the hydrogenation of o- and m-methylanisole, the Rh nanoparticles showed higher catalytic activity than the corresponding Ru nanoparticles. The Ir nanoparticles presented the lowest catalytic activity of the series. In all cases, the hydrogenation of o-methylanisole gave total selectivity for the cis-product, however, the ee of the product was always less than 6 %. A maximum of 81 % cis-selectivity was obtained for the hydrogenation of m-methylanisole, however, no asymmetric induction was observed. These results show that the catalytic activity is affected by a combination of influences from the substrate, the diphosphite ligands, and the metallic nanoparticles.

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