Role of the Metal Ion in Bio-Inspired Hydrogenase Models: Investigation of a Homodinuclear FeFe Complex vs Its Heterodinuclear NiFe Analogue

Autor: Lianke Wang, Christian Philouze, Alexandre Barrozo, Carole Duboc, Franc Meyer, Jennifer Fize, Maylis Orio, Marcello Gennari, Serhiy Demeshko, Vincent Artero
Přispěvatelé: Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut für Anorganische Chemie, Georg-August-University = Georg-August-Universität Göttingen, ANR-16-CE92-0012,NiFemim,Catalyseurs bio-inspirés de l'hydrogénase à [NiFe] pour la production d'hydrogène.(2016), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Georg-August-University [Göttingen]
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Zdroj: ACS Catalysis
ACS Catalysis, 2020, 10 (1), pp.177-186. ⟨10.1021/acscatal.9b03212⟩
ACS Catalysis, American Chemical Society, 2020, 10 (1), pp.177-186. ⟨10.1021/acscatal.9b03212⟩
ISSN: 2155-5435
DOI: 10.1021/acscatal.9b03212⟩
Popis: International audience; In nature, dihydrogen is catalytically produced or split by the [FeFe] and [NiFe] hydrogenases. Despite common structural features in their dinuclear active site, i.e., a thiolate-rich coordination sphere and CO/CN– ligation, the synergetic way, in which the two metal sites act during catalysis, is specific for each enzyme. With the aim of understanding the role of the nature of the metal (Fe vs Ni), we report on a homodinuclear FeFe complex, a parent of a previously reported NiFe complex, to compare their electrocatalytic activity for H2 production. The di-iron complex [(CO)LN2S2FeIIFeII(CO)Cp]+ (with LN2S2 = 2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1-diphenylethanethiolate and Cp = cyclopentadienyl) has been synthesized and fully characterized. In the solid state, it contains two CO ligands: one bound to the {FeCp} moiety in a semibridging manner and one terminally bound to the {FeLN2S2} moiety. This dinuclear iron complex is thus not isostructural to [LN2S2NiIIFeII(CO)Cp]+, which contains a single CO ligand terminally bound to the Fe site. However, at low concentrations in MeCN solutions, the CO ligand coordinated to the {FeLN2S2} moiety is removed and the CO ligand bound to the {FeCp} moiety becomes fully bridging between the two Fe sites. Under such conditions, the di-iron complex displays similar catalytic performances to the parent NiFe complex (a comparable overpotential, η = 730 and 690 mV, and TON = 15 and 16, respectively). Cyclic voltammetry data give direct experimental evidence for an E[ECEC] mechanism, which was also previously proposed for the NiFe complex. However, the structure of the one-electron reduced species, the entry point of the catalytic cycle, slightly differs for the two systems: in [LN2S2NiI(CO)FeIICp], this is valence localized species on the site Ni and the CO ligand bridges the two metal ions, while in [(CO)LN2S2FeFeCp], this is a type II–III mixed-valence species with the CO terminally bound to the {FeLN2S2} unit.
Databáze: OpenAIRE
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