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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 LU ; Pickett, Christopher J. and De Gioia, Luca (2008) In Comptes Rendus. Chimie 11(8). p.834-841
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
density, functional theory, biomimetic models, hydrogenase, bioinorganic chemistry, iron
in
Comptes Rendus. Chimie
volume
11
issue
8
pages
834 - 841
publisher
Elsevier
external identifiers
  • wos:000258393100005
  • scopus:47949122179
ISSN
1631-0748
DOI
10.1016/j.crci.2008.04.010
language
English
LU publication?
yes
id
46231753-1171-4eef-ba44-a840fe5ceb16 (old id 1252898)
date added to LUP
2008-11-03 13:02:57
date last changed
2017-01-01 04:41:27
@article{46231753-1171-4eef-ba44-a840fe5ceb16,
  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.},
  author       = {Bruschi, Maurizio and Greco, Claudio and Zampella, Giuseppe and Ryde, Ulf and Pickett, Christopher J. and De Gioia, Luca},
  issn         = {1631-0748},
  keyword      = {density,functional theory,biomimetic models,hydrogenase,bioinorganic chemistry,iron},
  language     = {eng},
  number       = {8},
  pages        = {834--841},
  publisher    = {Elsevier},
  series       = {Comptes Rendus. Chimie},
  title        = {A DFT investigation on structural and redox properties of a synthetic Fe6S6 assembly closely related to the [FeFe]-hydrogenases active site},
  url          = {http://dx.doi.org/10.1016/j.crci.2008.04.010},
  volume       = {11},
  year         = {2008},
}