Issue 4, 2003

All-iron hydrogenase: synthesis, structure and properties of {2Fe3S}-assemblies related to the di-iron sub-site of the H-cluster

Abstract

Tripodal dithiolate thioether ligands MeC(CH2SH)2CH2SR (R = Me or Ph) provide a route to {2Fe3S}-complexes and syntheses are described. X-Ray crystal structures for two {2Fe3S}-pentacarbonyl derivatives and that for the first carbonyl cyanide are reported, together with temperature dependent 1H-NMR, Mössbauer, FTIR and redox potential data. The NMR data establish fluctionality associated with inversion at the thioether sulfur in the carbonyl complexes. The Mössbauer data affirm that the coordination environment of the two iron atoms in a dicyanide bridging carbonyl intermediate are differentiated. Bridging carbonyl intermediates have been structurally and spectroscopically identified in resting and CO inhibited forms of the sub-site of all-iron hydrogenases; the observation of a thermally unstable {2Fe3S}-bridging carbonyl intermediate is discussed in this context.

Graphical abstract: All-iron hydrogenase: synthesis, structure and properties of {2Fe3S}-assemblies related to the di-iron sub-site of the H-cluster

Supplementary files

Article information

Article type
Paper
Submitted
03 Oct 2002
Accepted
03 Dec 2002
First published
21 Jan 2003

Dalton Trans., 2003, 586-595

All-iron hydrogenase: synthesis, structure and properties of {2Fe3S}-assemblies related to the di-iron sub-site of the H-cluster

M. Razavet, S. C. Davies, D. L. Hughes, J. E. Barclay, D. J. Evans, S. A. Fairhurst, X. Liu and C. J. Pickett, Dalton Trans., 2003, 586 DOI: 10.1039/B209690K

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