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http://hdl.handle.net/20.500.12188/16155
Наслов: | 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: | сеп-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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