Volume 148, 2011

Protonation of [FeFe]-hydrogenase sub-site analogues: revealing mechanism using FTIR stopped-flow techniques

Abstract

The formation of transient metal hydride(s) at the metallo-sulfur active sites of [FeFe]-hydrogenase is implicated in both hydrogen evolution and uptake reactions. Stopped-flow spectroscopic techniques can provide insight into the reactivity patterns of model {2Fe2S} sub-sites towards protons, and this information contributes to understanding the nature of the biological systems. In this study we have focussed on the influence of the nature of the bridging dithiolate ligand in influencing the kinetics and activation energy parameters for protonation in synthetic sub-sites including Fe2{μ-[S(CH2)nS]}(CO)4(PMe3)2 [n = 2, ethane-1,2-dithiolate (edt) or n = 3, propane-1,3-dithiolate (pdt)], Fe2[(μ-SCH2)2NH](CO)4(PMe3)2 and (NEt4)2{Fe2[(μ-SCH2)2NH](CO)4(CN)2}. Notably we find that (i) the presence of a nitrogen in the dithiolate bridge does not accelerate metal–metal bond protonation, and that (ii) immobilisation of (NEt4)2[Fe2(μ-pdt)(CO)4(CN)2] in a polymer matrix stabilises otherwise short-lifetime protonation products.

Article information

Article type
Paper
Submitted
30 Mar 2010
Accepted
13 Apr 2010
First published
18 Aug 2010

Faraday Discuss., 2011,148, 359-371

Protonation of [FeFe]-hydrogenase sub-site analogues: revealing mechanism using FTIR stopped-flow techniques

J. A. Wright, L. Webster, A. Jablonskytė, P. M. Woi, S. K. Ibrahim and C. J. Pickett, Faraday Discuss., 2011, 148, 359 DOI: 10.1039/C004692B

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