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Carbon Dioxide Reduction Catalyzed by Dinuclear Ruthenium Polypyridyl Complexes

Authors

  • Takashi Ono,

    1. Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228
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  • Dr. Nora Planas,

    1. Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)
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  • Dr. Pere Miró,

    1. Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)
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  • Dr. Mehmed Z. Ertem,

    1. Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)
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  • Eduardo C. Escudero-Adán,

    1. Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228
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  • Dr. Jordi Benet-Buchholz,

    1. Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228
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  • Prof. Dr. Laura Gagliardi,

    Corresponding author
    1. Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)
    • Laura Gagliardi, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Christopher J. Cramer, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228

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  • Prof. Dr. Christopher J. Cramer,

    Corresponding author
    1. Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)
    • Laura Gagliardi, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Christopher J. Cramer, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228

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  • Prof. Dr. Antoni Llobet

    Corresponding author
    1. Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228
    2. Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona (Spain)
    • Laura Gagliardi, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Christopher J. Cramer, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia, Av. Països Catalans 16, 43007 Tarragona (Spain), Fax: (+34) 977-902-228

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Abstract

Dinuclear ruthenium complexes [(Ru(bid))2(μ-bpp)(μ-OAc)] and [(Ru(trpy))2(μ-bpp)(μ-X)]2+ [X=Cl, OAc, and OCHO; bpp=3,5-bis(2-pyridyl)pyrazolato; bid=(1Z,3Z)-1,3-bis(pyridin-2-ylmethylene)isoindolin-2-ide; trpy=2,2':6',2“-terpyridine] were tested as catalysts for the hydrogenative reduction of carbon dioxide in the solvent 2,2,2-trifluoroethanol in the presence of excess amine (triethylamine). Significant amounts of formic acid were produced by these catalysts, and a kinetic analysis based on initial rate constants was performed. These catalytic systems were investigated by using DFT calculations to elucidate the hydrogenative reduction mechanism. The results are compared with those obtained with previously reported mononuclear catalyst counterparts.

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