Dual electron uptake by simultaneous iron and ligand reduction in an N-heterocyclic carbene substituted [FeFe] hydrogenase model compound

Jesse W Tye; Jonghyuk Lee; Hsiao-Wan Wang; Rosario Mejia-Rodriguez; Joseph H Reibenspies; Michael B Hall; Marcetta Y Darensbourg

doi:10.1021/ic050402d

Dual electron uptake by simultaneous iron and ligand reduction in an N-heterocyclic carbene substituted [FeFe] hydrogenase model compound

Inorg Chem. 2005 Aug 8;44(16):5550-2. doi: 10.1021/ic050402d.

Authors

Jesse W Tye¹, Jonghyuk Lee, Hsiao-Wan Wang, Rosario Mejia-Rodriguez, Joseph H Reibenspies, Michael B Hall, Marcetta Y Darensbourg

Affiliation

¹ Department of Chemistry, Texas A&M University, College Station, 77843-3255, USA.

PMID: 16060601
DOI: 10.1021/ic050402d

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.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Binding Sites
Catalysis
Crystallography, X-Ray
Hydrogenase / chemistry*
Iron / chemistry*
Ligands
Models, Molecular*
Molecular Conformation
Oxidation-Reduction

Substances

Ligands
Iron
Hydrogenase