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Secondary bonding interactions in biomimetic [2Fe-2S] clusters

Ballmann, Joachim; Dechert, Sebastian; Bill, Eckhard; Ryde, Ulf LU and Meyer, Franc (2008) In Inorganic Chemistry 47(5). p.1586-1596
Abstract
A series of synthetic [2Fe-2S] complexes with terminal thiophenolate ligands and tethered ether or thioether moieties has been prepared and investigated in order to provide models for the potential interaction of additional donor atoms with the Fe atoms in biological [2Fe-2S] clusters. X-ray crystal structures have been determined for six new complexes that feature appended Et (1(C)), OMe (1(O)), or SMe (1(S)) groups, or with a methylene group (2(C)), an ether-O (2(O)), or an thioether-S (2(S)) linking two aryl group. The latter two systems provide a constrained chelate arrangement that induces secondary bonding interactions with the ether-O and thioether-S, which is confirmed by density functional theory (DFT) calculations that also... (More)
A series of synthetic [2Fe-2S] complexes with terminal thiophenolate ligands and tethered ether or thioether moieties has been prepared and investigated in order to provide models for the potential interaction of additional donor atoms with the Fe atoms in biological [2Fe-2S] clusters. X-ray crystal structures have been determined for six new complexes that feature appended Et (1(C)), OMe (1(O)), or SMe (1(S)) groups, or with a methylene group (2(C)), an ether-O (2(O)), or an thioether-S (2(S)) linking two aryl group. The latter two systems provide a constrained chelate arrangement that induces secondary bonding interactions with the ether-O and thioether-S, which is confirmed by density functional theory (DFT) calculations that also reveal significant spin density on those fifth donor atoms. Structural consequences of the secondary bonding interactions are analyzed in detail, and effects on the spectroscopic and electronic properties are probed by UV-vis, Mossbauer, and H-1 NMR spectroscopy, as well by SQUID measurements and cyclic voltammetry. The potential relevance of the findings for biological [2Fe-2S] sites is considered. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
47
issue
5
pages
1586 - 1596
publisher
The American Chemical Society
external identifiers
  • wos:000253428500023
  • scopus:41849088837
ISSN
1520-510X
DOI
10.1021/ic702095a
language
English
LU publication?
yes
id
1f11e829-752a-4db1-9f29-1b25fc576487 (old id 1193781)
date added to LUP
2008-09-09 18:06:54
date last changed
2017-04-23 03:28:15
@article{1f11e829-752a-4db1-9f29-1b25fc576487,
  abstract     = {A series of synthetic [2Fe-2S] complexes with terminal thiophenolate ligands and tethered ether or thioether moieties has been prepared and investigated in order to provide models for the potential interaction of additional donor atoms with the Fe atoms in biological [2Fe-2S] clusters. X-ray crystal structures have been determined for six new complexes that feature appended Et (1(C)), OMe (1(O)), or SMe (1(S)) groups, or with a methylene group (2(C)), an ether-O (2(O)), or an thioether-S (2(S)) linking two aryl group. The latter two systems provide a constrained chelate arrangement that induces secondary bonding interactions with the ether-O and thioether-S, which is confirmed by density functional theory (DFT) calculations that also reveal significant spin density on those fifth donor atoms. Structural consequences of the secondary bonding interactions are analyzed in detail, and effects on the spectroscopic and electronic properties are probed by UV-vis, Mossbauer, and H-1 NMR spectroscopy, as well by SQUID measurements and cyclic voltammetry. The potential relevance of the findings for biological [2Fe-2S] sites is considered.},
  author       = {Ballmann, Joachim and Dechert, Sebastian and Bill, Eckhard and Ryde, Ulf and Meyer, Franc},
  issn         = {1520-510X},
  language     = {eng},
  number       = {5},
  pages        = {1586--1596},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {Secondary bonding interactions in biomimetic [2Fe-2S] clusters},
  url          = {http://dx.doi.org/10.1021/ic702095a},
  volume       = {47},
  year         = {2008},
}