title: Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase.
abstract: Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2evolution (second-order rate constant of 2.5 × 104M-1s-1; turnover frequency of 250 s-1at 10 mM H+concentration) from mildly acidic solutions.
authors: Univ. Grenoble Alpes, CNRS UMR 5250, DCM, F-38000 Grenoble, France.|Univ. Grenoble Alpes, CNRS UMR 5249, CEA, Laboratoire de Chimie et Biologie des Métaux, F-38000 Grenoble, France.
authors: Deborah
authors: D
authors: Brazzolotto
authors: Univ. Grenoble Alpes, CNRS UMR 5250, DCM, F-38000 Grenoble, France.
authors: Marcello
authors: M
authors: Gennari
authors: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, Laboratoire de Chimie et Biologie des Métaux, F-38000 Grenoble, France.
authors: Nicolas
authors: N
authors: Queyriaux
authors: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, Laboratoire de Chimie et Biologie des Métaux, F-38000 Grenoble, France.
authors: Trevor R
authors: TR
authors: Simmons
authors: Univ. Grenoble Alpes, INAC-LCIB, F-38000 Grenoble, France.|CEA, DRF-INAC-SyMMES, Reconnaissance Ionique et Chimie de Coordination, F-38000 Grenoble, France.
authors: Jacques
authors: J
authors: Pécaut
authors: Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors: Serhiy
authors: S
authors: Demeshko
authors: Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.|International Center for Advanced Studies of Energy Conversion (ICASEC), Georg-August-University, D-37077 Göttingen, Germany.
authors: Franc
authors: F
authors: Meyer
authors: Institut des Sciences Moléculaires de Marseille, Aix Marseille Université, CNRS, Centrale Marseille, ISM2 UMR 7313, 13397, Marseille, France.
authors: Maylis
authors: M
authors: Orio
authors: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, Laboratoire de Chimie et Biologie des Métaux, F-38000 Grenoble, France.
authors: Vincent
authors: V
authors: Artero
authors: Univ. Grenoble Alpes, CNRS UMR 5250, DCM, F-38000 Grenoble, France.
authors: Carole
authors: C
authors: Duboc
mesh_terms: D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D020134:Catalytic Domain; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D006859:Hydrogen / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D011522:Protons
chemical_list: D056831:Coordination Complexes; D011522:Protons; D009532:Nickel; D006859:Hydrogen; C043296:nickel-iron hydrogenase; D006864:Hydrogenase