Dual electron uptake by simultaneous iron and ligand reduction in an N-heterocyclic carbene substituted [FeFe] hydrogenase model compound.
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.
Tye
Jesse W
JW
Department of Chemistry, Texas A&M University, College Station, 77843-3255, USA.
Lee
Jonghyuk
J
Wang
Hsiao-Wan
HW
Mejia-Rodriguez
Rosario
R
Reibenspies
Joseph H
JH
Hall
Michael B
MB
Darensbourg
Marcetta Y
MY
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
D008024:Ligands; D007501:Iron; D006864:Hydrogenase