title: Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study.
abstract: Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Maria
authors.initials: M
authors.lastname: Gomez-Mingot
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Jean-Philippe
authors.initials: JP
authors.lastname: Porcher
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Tanya K
authors.initials: TK
authors.lastname: Todorova
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Thibault
authors.initials: T
authors.lastname: Fogeron
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Caroline
authors.initials: C
authors.lastname: Mellot-Draznieks
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Yun
authors.initials: Y
authors.lastname: Li
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Université Pierre et Marie Curie-Paris 6, Collège de France , 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
mesh_terms: D032701:Biomimetics; D002384:Catalysis; D055664:Electrochemical Techniques; D005560:Formate Dehydrogenases / Q000737:chemistry / Q000378:metabolism; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D011522:Protons; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011522:Protons; D013438:Sulfhydryl Compounds; D006859:Hydrogen; D005560:Formate Dehydrogenases; D014414:Tungsten