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Iron-sulfur clusters: Why iron?

Jensen, Kasper LU (2006) In Journal of Inorganic Biochemistry 100(8). p.1436-1439
Abstract
This communication addresses a simple question by means of density functional calculations: Why is iron used as the metal in. iron-sulfur clusters? While there may be several answers to this question, it is shown here that one feature - the well-defined inner-sphere reorganization energy of self-exchange electron transfer - is very much favored in iron-sulfur clusters as opposed to metal substituted analogues of Mn, Co, Ni, and Cu. Furthermore, the conclusion holds for both 1Fe and 2Fe type iron-sulfur clusters. The results show that only iron provides a small inner-sphere reorganization energy of 21 kJ/mol in 1Fe (rubredoxin) and 46 kJ/mol in 2Fe (ferredoxin) models, whereas other metal ions exhibit values in the range 57-135 kJ/mol (1Fe)... (More)
This communication addresses a simple question by means of density functional calculations: Why is iron used as the metal in. iron-sulfur clusters? While there may be several answers to this question, it is shown here that one feature - the well-defined inner-sphere reorganization energy of self-exchange electron transfer - is very much favored in iron-sulfur clusters as opposed to metal substituted analogues of Mn, Co, Ni, and Cu. Furthermore, the conclusion holds for both 1Fe and 2Fe type iron-sulfur clusters. The results show that only iron provides a small inner-sphere reorganization energy of 21 kJ/mol in 1Fe (rubredoxin) and 46 kJ/mol in 2Fe (ferredoxin) models, whereas other metal ions exhibit values in the range 57-135 kJ/mol (1Fe) and 94-140 kJ/mol (2Fe). This simple result provides an important, although partial, explanation why iron alone is used in this type of clusters. The results can be explained by simple orbital rules of electron transfer, which state that the occupation of anti-bonding orbitals should not change during the redox reactions. This rule immediately suggests good and poor electron carriers. (c) 2006 Elsevier Inc. All rights reserved. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
orbital rules, transfer, electron, Marcus theory, iron-sulfur cluster, reorganization energy
in
Journal of Inorganic Biochemistry
volume
100
issue
8
pages
1436 - 1439
publisher
Elsevier
external identifiers
  • wos:000239981800017
  • pmid:16716401
  • scopus:33745594574
ISSN
1873-3344
DOI
10.1016/j.jinorgbio.2006.03.016
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
24e95981-d3bb-4ca8-99ed-457ebde698a8 (old id 395098)
date added to LUP
2016-04-01 17:14:45
date last changed
2021-02-17 03:17:57
@article{24e95981-d3bb-4ca8-99ed-457ebde698a8,
  abstract     = {This communication addresses a simple question by means of density functional calculations: Why is iron used as the metal in. iron-sulfur clusters? While there may be several answers to this question, it is shown here that one feature - the well-defined inner-sphere reorganization energy of self-exchange electron transfer - is very much favored in iron-sulfur clusters as opposed to metal substituted analogues of Mn, Co, Ni, and Cu. Furthermore, the conclusion holds for both 1Fe and 2Fe type iron-sulfur clusters. The results show that only iron provides a small inner-sphere reorganization energy of 21 kJ/mol in 1Fe (rubredoxin) and 46 kJ/mol in 2Fe (ferredoxin) models, whereas other metal ions exhibit values in the range 57-135 kJ/mol (1Fe) and 94-140 kJ/mol (2Fe). This simple result provides an important, although partial, explanation why iron alone is used in this type of clusters. The results can be explained by simple orbital rules of electron transfer, which state that the occupation of anti-bonding orbitals should not change during the redox reactions. This rule immediately suggests good and poor electron carriers. (c) 2006 Elsevier Inc. All rights reserved.},
  author       = {Jensen, Kasper},
  issn         = {1873-3344},
  language     = {eng},
  number       = {8},
  pages        = {1436--1439},
  publisher    = {Elsevier},
  series       = {Journal of Inorganic Biochemistry},
  title        = {Iron-sulfur clusters: Why iron?},
  url          = {http://dx.doi.org/10.1016/j.jinorgbio.2006.03.016},
  doi          = {10.1016/j.jinorgbio.2006.03.016},
  volume       = {100},
  year         = {2006},
}