High-valent nonheme iron-oxo species in biomimetic oxidations

Xiaopeng Shan, Lawrence Que

Research output: Contribution to journalReview articlepeer-review

166 Scopus citations

Abstract

High valent iron-oxo species are often invoked as the key oxidizing agents in the catalytic cycles of oxygen activating nonheme iron enzymes, and three of these intermediates have in fact been characterized. To gain further insight into such species, a number of biomimetic complexes have been designed and investigated as functional models for these enzymes. Progress since 2000 is summarized in this review. Many of the model complexes discussed in this review carry out oxidative transformations of relevance to the enzymatic reactions; however, the participation of a high-valent iron-oxo species (FeIV{double bond, long}O or FeV{double bond, long}O) can only be inferred. Arguments in support of a metal-based oxidant (rather than an oxygen radical species) usually hinge on the high conversion for the transformation and the nature of the reaction products, as well as the incorporation of label into these products from H218O or related species. Within this time period, the first bona fide nonheme FeIV{double bond, long}O complexes have been generated and identified spectroscopically, three of which are crystallographically characterized. Taken together, these studies emphasize the important role the supporting polydentate ligand plays in eliciting the desired high-valent iron-oxo chemistry.

Original languageEnglish (US)
Pages (from-to)421-433
Number of pages13
JournalJournal of Inorganic Biochemistry
Volume100
Issue number4
DOIs
StatePublished - Apr 1 2006

Keywords

  • High-valent
  • Iron-catalyzed oxidation
  • Iron-oxo
  • Nonheme

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