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Cp*-Ruthenium–Nickel-Based H2-Evolving Electrocatalysts as Bio-inspired Models of NiFe Hydrogenases

Authors

  • Sigolène Canaguier,

    1. Laboratoire de Chimie et Biologie des Métaux, Université Grenoble 1, CNRS UMR 5249, CEA DSV/iRTSV, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France, Fax: +33-4-38789124
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  • Marc Fontecave,

    1. Laboratoire de Chimie et Biologie des Métaux, Université Grenoble 1, CNRS UMR 5249, CEA DSV/iRTSV, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France, Fax: +33-4-38789124
    2. Collège de France, 11 place Marcellin-Berthelot, 75005 Paris, France
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  • Vincent Artero

    1. Laboratoire de Chimie et Biologie des Métaux, Université Grenoble 1, CNRS UMR 5249, CEA DSV/iRTSV, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France, Fax: +33-4-38789124
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Abstract

Three dinuclear nickel–ruthenium complexes [Ni(xbsms)RuCp*(L)](PF6) [H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene; Cp* = pentamethylcyclopentadienyl; L = CH3CN, CO and O2] are reported that act as bio-inspired mimics of NiFe hydrogenases. Because of an increased electron density at the metal centres in comparison with the previously described [Ni(xbsms)RuCp(L)](PF6) (Cp = cyclopentadienyl) analogues, these compounds catalyze the evolution of hydrogen from Et3NH+ in DMF with an overpotential reduced by around 50 mV, thereby corroborating a previously established structure–function relationship [Eur. J. Inorg. Chem.2007, 18, 2613–2626; Chem. Eur. J.2009, 15, 9350–9364]. In addition, the steric protection provided by the bulky Cp* ligand results in an increased catalytic rate and stability upon cycling.

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