Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer

Shunichi Fukuzumi, Yuma Morimoto, Hiroaki Kotani, Panće Naumov, Yong Min Lee, Wonwoo Nam

Research output: Contribution to journalArticle

Abstract

Critical biological electron-transfer processes involving high-valent oxometal chemistry occur widely, for example in haem proteins [oxoiron(IV); FeIV (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 Ca2+ and Sc3+ to a non-haem oxoiron(IV) complex, [(TMC)FeIV (O)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). As determined by X-ray diffraction analysis, an oxo-Sc3+ 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.

Original languageEnglish (US)
Pages (from-to)756-759
Number of pages4
JournalNature chemistry
Volume2
Issue number9
DOIs
StatePublished - Sep 2010

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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