Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12188/16155
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dc.contributor.authorFukuzumi, Shunichien_US
dc.contributor.authorMorimoto, Yumaen_US
dc.contributor.authorKotani, Hiroakien_US
dc.contributor.authorNaumov, Panceen_US
dc.contributor.authorLee, Yong-Minen_US
dc.contributor.authorNam, Wonwooen_US
dc.date.accessioned2022-01-14T09:10:08Z-
dc.date.available2022-01-14T09:10:08Z-
dc.date.issued2010-09-
dc.identifier.urihttp://hdl.handle.net/20.500.12188/16155-
dc.description.abstractCritical 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.en_US
dc.language.isoenen_US
dc.publisherSpringer Science and Business Media LLCen_US
dc.relation.ispartofNature chemistryen_US
dc.titleCrystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transferen_US
dc.identifier.doi10.1038/nchem.731-
dc.identifier.urlhttp://www.nature.com/articles/nchem.731.pdf-
dc.identifier.urlhttp://www.nature.com/articles/nchem.731-
dc.identifier.urlhttp://www.nature.com/articles/nchem.731.pdf-
dc.identifier.volume2-
dc.identifier.issue9-
item.fulltextNo Fulltext-
item.grantfulltextnone-
Appears in Collections:Faculty of Natural Sciences and Mathematics: Journal Articles
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