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Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer

Title
Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
Authors
Fukuzumi S.Morimoto Y.Kotani H.Naumov P.Lee Y.-M.Nam W.
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2010
Journal Title
Nature Chemistry
ISSN
1755-4330JCR Link
Citation
vol. 2, no. 9, pp. 756 - 759
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Critical biological electron-transfer processes involving high-valent oxometal chemistry occur widely, for example in haem proteins [oxoiron(IV); FeIV (O)] and in photosystem II. Photosystem II involves Ca 2+ as well as high-valent oxomanganese cluster species. However, there is no example of an interaction between metal ions and oxoiron(IV) complexes. Here, we report new findings concerning the binding of the redox-inactive metal ions Ca2+ and Sc3+ to a non-haem oxoiron(IV) complex, [(TMC)FeIV (O)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). As determined by X-ray diffraction analysis, an oxo-Sc3+ interaction leads to a structural distortion of the oxoiron(IV) moiety. More importantly, this interaction facilitates a two-electron reduction by ferrocene, whereas only a one-electron reduction process occurs without the metal ions. This control of redox behaviour provides valuable mechanistic insights into oxometal redox chemistry, and suggests a possible key role that an auxiliary Lewis acid metal ion could play in nature, as in photosystem II. © 2010 Macmillan Publishers Limited. All rights reserved.
DOI
10.1038/nchem.731
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자연과학대학 > 화학·나노과학전공 > Journal papers
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