title: Dual electron uptake by simultaneous iron and ligand reduction in an N-heterocyclic carbene substituted [FeFe] hydrogenase model compound.
abstract: An N-heterocyclic carbene containing [FeFe]H(2)ase model complex, whose X-ray structure displays an apical carbene, shows an unexpected two-electron reduction to be involved in its electrocatalytic dihydrogen production. Density functional calculations show, in addition to a one-electron Fe-Fe reduction, that the aryl-substituted N-heterocyclic carbene can accept a second electron more readily than the Fe-Fe manifold. The juxtaposition of these two one-electron reductions resembles the [FeFe]H(2)ase active site with an FeFe di-iron unit joined to the electroactive 4Fe4S cluster.
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, 77843-3255, USA.
authors.forename: Jesse W
authors.initials: JW
authors.lastname: Tye
authors.forename: Jonghyuk
authors.initials: J
authors.lastname: Lee
authors.forename: Hsiao-Wan
authors.initials: HW
authors.lastname: Wang
authors.forename: Rosario
authors.initials: R
authors.lastname: Mejia-Rodriguez
authors.forename: Joseph H
authors.initials: JH
authors.lastname: Reibenspies
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
authors.forename: Marcetta Y
authors.initials: MY
authors.lastname: Darensbourg
mesh_terms: D001665:Binding Sites; D002384:Catalysis; D018360:Crystallography, X-Ray; D006864:Hydrogenase / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction
chemical_list: D008024:Ligands; D007501:Iron; D006864:Hydrogenase