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Issue 22, 2009
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Critical aspects of [NiFe]hydrogenase ligand composition

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Structural analysis of the resting state of [NiFe]hydrogenase ([NiFe]H2ase) shows that the active site has a characteristic bis(μ-thiolato)NiFe unit, where the Ni atom and the Fe atom are bridged by an undetermined oxygen-bearing ligand. This ligand probably derives from the aqueous solvent and is therefore most likely to be H2O, OH or O2−. Here, we compare the reactivities of a NiFe and a NiRu complex when bearing either acetonitrile or aqueous ligands and demonstrate the critical role of an aqueous ligand in hydrogenase and its mimics. We also make observations on the necessity of organometallic metal–carbon bonds to the supporting frameworks.

Graphical abstract: Critical aspects of [NiFe]hydrogenase ligand composition

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The article was received on 03 Nov 2008, accepted on 24 Dec 2008 and first published on 06 Feb 2009

Article type: Paper
DOI: 10.1039/B819395A
Dalton Trans., 2009, 4304-4309

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    Critical aspects of [NiFe]hydrogenase ligand composition

    K. Ichikawa, T. Matsumoto and S. Ogo, Dalton Trans., 2009, 4304
    DOI: 10.1039/B819395A

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