Characterization of a high-spin non-heme FeIII-OOH intermediate and its quantitative conversion to an FeIV=O complex

Feifei Li, Katlyn K. Meier, Matthew A. Cranswick, Mrinmoy Chakrabarti, Katherine M. Van Heuvelen, Eckard Münck, Lawrence Que

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We have generated a high-spin FeIII-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This FeIII-OOH species can be converted quantitatively to an FeIV=O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong FeIII-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin FeIII-peroxo intermediates of non-heme iron enzymes may be promoted.

Original languageEnglish (US)
Pages (from-to)7256-7259
Number of pages4
JournalJournal of the American Chemical Society
Issue number19
StatePublished - May 18 2011


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