title: A Bioinspired Molybdenum Complex as a Catalyst for the Photo- and Electroreduction of Protons.
abstract: A molybdenum-dithiolene-oxo complex was prepared as a model of some active sites of Mo/W-dependent enzymes. The ligand, a quinoxaline-pyran-fused dithiolene, mimics molybdopterin present in these active sites. For the first time, this type of complex was shown to be active as a catalyst for the photoreduction of protons with excellent turnover numbers (500) and good stability in aqueous/organic media and for the electroreduction of protons in acetonitrile with remarkable rate constants (1030 s(-1) at -1.3 V versus Ag/AgCl). DFT calculations provided insight into the catalytic cycle of the reaction, suggesting that the oxo ligand plays a key role in proton exchange. These results provide a basis to optimize this new class of H2 -evolving catalysts.
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris 6, 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, Collège de France, Université Paris 6, 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, Collège de France, Université Paris 6, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05 (France).
authors.forename: Maria
authors.initials: M
authors.lastname: Gomez-Mingot
authors.affiliation: Sorbonne Universités, UPMC Université Paris 6, Institut Parisien de Chimie Moléculaire, UMR 8232 CNRS, 4 place Jussieu, 75252 Paris Cedex 5 (France).
authors.forename: Etienne
authors.initials: E
authors.lastname: Derat
authors.affiliation: Sorbonne Universités, UPMC Université Paris 6, Institut Parisien de Chimie Moléculaire, UMR 8232 CNRS, 4 place Jussieu, 75252 Paris Cedex 5 (France).
authors.forename: Lise-Marie
authors.initials: LM
authors.lastname: Chamoreau
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris 6, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05 (France). yun.xu-li@college-de-france.fr.
authors.forename: Yun
authors.initials: Y
authors.lastname: Li
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris 6, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05 (France). marc.fontecave@college-de-france.fr.
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
keywords: density functional calculations; dithiolene ligands; homogeneous catalysis; hydrogen evolution reaction; molybdenum