Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12188/16155
Title: Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
Authors: Fukuzumi, Shunichi
Morimoto, Yuma
Kotani, Hiroaki
Naumov, Pance
Lee, Yong-Min
Nam, Wonwoo
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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