A DFT investigation on structural and redox properties of a synthetic Fe6S6 assembly closely related to the [FeFe]-hydrogenases active site

Bruschi, Maurizio, Greco, Claudio, Zampella, Giuseppe, Ryde, Ulf, Pickett, Christopher and De Gioia, Luca (2008) A DFT investigation on structural and redox properties of a synthetic Fe6S6 assembly closely related to the [FeFe]-hydrogenases active site. Comptes Rendus Chimie, 11 (8). pp. 834-841. ISSN 1878-1543

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Abstract

In the present contribution, a density functional theory (DFT) investigation is described regarding a recently synthesized Fe6S6 complex – see C. Tard, X. Liu, S.K. Ibrahim, M. Bruschi, L. De Gioia, S.C. Davies, X. Yang, L.-S. Wang, G. Sawers, C.J. Pickett, Nature 433 (2005) 610 – that is structurally and functionally related to the [FeFe]-hydrogenases active site (the so-called H-cluster, which includes a binuclear subsite directly involved in catalysis and an Fe4S4 cubane). The analysis of relative stabilities and atomic charges of different isomers evidenced that the structural and redox properties of the synthetic assembly are significantly different from those of the enzyme active site. A comparison between the hexanuclear cluster and simpler synthetic diiron models is also described; the results of such a comparison indicated that the cubane moiety can favour the stabilization of the cluster in a structure closely resembling the H-cluster geometry when the synthetic Fe6S6 complex is in its dianionic state. However, the opposite effect is observed when the synthetic cluster is in its monoanionic form.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
University of East Anglia > Faculty of Science > Research Groups > Biophysical Chemistry
University of East Anglia > Faculty of Science > Research Groups > Synthetic Chemistry
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Depositing User: Rachel Smith
Date Deposited: 23 Mar 2011 15:45
Last Modified: 25 Jul 2018 05:09
URI: https://ueaeprints.uea.ac.uk/id/eprint/27080
DOI: 10.1016/j.crci.2008.04.010

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