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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1252898
- author
- Bruschi, Maurizio
; Greco, Claudio
; Zampella, Giuseppe
; Ryde, Ulf
LU
; Pickett, Christopher J.
and De Gioia, Luca
- organization
- publishing date
- 2008
- 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
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 46231753-1171-4eef-ba44-a840fe5ceb16 (old id 1252898)
- date added to LUP
- 2016-04-01 11:56:46
- date last changed
- 2023-02-07 02:35:35
@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}},
keywords = {{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 = {{https://lup.lub.lu.se/search/files/136745692/112_feh2ase_comptes.pdf}},
doi = {{10.1016/j.crci.2008.04.010}},
volume = {{11}},
year = {{2008}},
}