A Bioinspired Molybdenum Complex as a Catalyst for the Photo‐ and Electroreduction of Protons |
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| Authors: | Jean‐Philippe Porcher Thibault Fogeron Dr Maria Gomez‐Mingot Dr Etienne Derat Lise‐Marie Chamoreau Dr Yun Li Prof Marc Fontecave |
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| Institution: | 1. Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris 6, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05 (France);2. Sorbonne Universités, UPMC Université Paris 6, Institut Parisien de Chimie Moléculaire, UMR 8232 CNRS, 4 place Jussieu, 75252 Paris Cedex 5 (France) |
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| 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. |
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| Keywords: | density functional calculations dithiolene ligands homogeneous catalysis hydrogen evolution reaction molybdenum |
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