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,next term 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.

Bruschi, M., Greco, C., Zampella, G., Ryde, U., Pickett, C., DE GIOIA, L. (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), 834-841 [10.1016/j.crci.2008.04.010].

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;DE GIOIA, LUCA
2008

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,next term 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.
Articolo in rivista - Articolo scientifico
Bioinorganic chemistry; Iron; Hydrogenase; Biomimetic models; Density functional theory
English
834
841
8
Bruschi, M., Greco, C., Zampella, G., Ryde, U., Pickett, C., DE GIOIA, L. (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), 834-841 [10.1016/j.crci.2008.04.010].
Bruschi, M; Greco, C; Zampella, G; Ryde, U; Pickett, C; DE GIOIA, L
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/3870
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