Issue 6, 2009

Unusual formation of a [NiSFe2(CO)6] cluster: a structural model for the inactive form of [NiFe] hydrogenase

Abstract

The synthesis and characterisation of the trinuclear Ni–Fe complex [Ni(L2)SFe2(CO)6] (1) formed from the reaction of [Ni(L1)] with Fe3(CO)12 is described. The single-crystal X-ray structure of 1 shows Ni(II) bound to three thioether R2-S donors and bridged by a sulfide (S2−) group to two Fe(CO)3 units. 1 undergoes a reversible one-electron reduction process at E1/2 = −1.62 V vs. Fc+/Fc to generate 1, which has been characterised by UV-vis and IR spectroelectrochemistry and by EPR spectroscopy. DFT calculations on 1 and 1 reveal electronic structures that are delocalised across the NiFe2 core. The SOMO in 1 possesses Ni–Fe and Fe–Fe anti-bonding character and lies approximately in the plane defined by the equilateral triangle of Ni and Fe atoms. It possesses d-orbital contributions of 18.5, 15.0 and 19.8% for the Ni(1), Fe(1) and Fe(2) atoms, respectively. The NiS(sulfide) bond length in 1 [2.1654(7) Å] is identical to that for the bridging sulfide found in the oxidised inactive form of the [NiFe] hydrogenase from D. vulgaris (2.16 Å). Thus, 1 provides a useful comparison for biological [NiFe] centres bridged by sulfide donors.

Graphical abstract: Unusual formation of a [NiSFe2(CO)6] cluster: a structural model for the inactive form of [NiFe] hydrogenase

Supplementary files

Article information

Article type
Paper
Submitted
18 Aug 2008
Accepted
30 Sep 2008
First published
10 Dec 2008

Dalton Trans., 2009, 925-931

Unusual formation of a [NiSFe2(CO)6] cluster: a structural model for the inactive form of [NiFe] hydrogenase

A. Perra, Q. Wang, A. J. Blake, E. S. Davies, J. McMaster, C. Wilson and M. Schröder, Dalton Trans., 2009, 925 DOI: 10.1039/B814298J

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