Please use this identifier to cite or link to this item:
http://hdl.handle.net/20.500.12188/16155
DC Field | Value | Language |
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dc.contributor.author | Fukuzumi, Shunichi | en_US |
dc.contributor.author | Morimoto, Yuma | en_US |
dc.contributor.author | Kotani, Hiroaki | en_US |
dc.contributor.author | Naumov, Pance | en_US |
dc.contributor.author | Lee, Yong-Min | en_US |
dc.contributor.author | Nam, Wonwoo | en_US |
dc.date.accessioned | 2022-01-14T09:10:08Z | - |
dc.date.available | 2022-01-14T09:10:08Z | - |
dc.date.issued | 2010-09 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.12188/16155 | - |
dc.description.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. | en_US |
dc.language.iso | en | en_US |
dc.publisher | Springer Science and Business Media LLC | en_US |
dc.relation.ispartof | Nature chemistry | en_US |
dc.title | Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer | en_US |
dc.identifier.doi | 10.1038/nchem.731 | - |
dc.identifier.url | http://www.nature.com/articles/nchem.731.pdf | - |
dc.identifier.url | http://www.nature.com/articles/nchem.731 | - |
dc.identifier.url | http://www.nature.com/articles/nchem.731.pdf | - |
dc.identifier.volume | 2 | - |
dc.identifier.issue | 9 | - |
item.grantfulltext | none | - |
item.fulltext | No Fulltext | - |
Appears in Collections: | Faculty of Natural Sciences and Mathematics: Journal Articles |
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