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|Title:||Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer||Authors:||Fukuzumi, Shunichi
|Issue Date:||Sep-2010||Publisher:||Springer Science and Business Media LLC||Journal:||Nature chemistry||Abstract:||Critical biological electron-transfer processes involving high-valent oxometal chemistry occur widely, for example in haem proteins [oxoiron(IV); Fe(IV)(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 Ca(2+) and Sc(3+) to a non-haem oxoiron(IV) complex, [(TMC)Fe(IV)(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). As determined by X-ray diffraction analysis, an oxo-Sc(3+) 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.||URI:||http://hdl.handle.net/20.500.12188/16155||DOI:||10.1038/nchem.731|
|Appears in Collections:||Faculty of Natural Sciences and Mathematics: Journal Articles|
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