Substrate activation by iron superoxo intermediates

Wilfred A. van der Donk, Carsten Krebs, J. Martin Bollinger

Research output: Contribution to journalReview article


A growing number of non-heme-iron oxygenases and oxidases catalyze reactions for which the well-established mechanistic paradigm involving a single C-H-bond-cleaving intermediate of the Fe(IV)-oxo (ferryl) type [1] is insufficient to explain the chemistry. It is becoming clear that, in several of these cases, Fe(III)-superoxide complexes formed by simple addition of O2 to the reduced [Fe(II)] cofactor initiate substrate oxidation by abstracting hydrogen [2,3]. This substrate-oxidizing entry route into high-valent-iron intermediates makes possible an array of complex and elegant oxidation reactions without the consumption of valuable reducing equivalents. Examples of this novel mechanistic strategy are discussed with the goal of bringing forth unifying principles.

Original languageEnglish (US)
Pages (from-to)673-683
Number of pages11
JournalCurrent Opinion in Structural Biology
Issue number6
StatePublished - Dec 1 2010


ASJC Scopus subject areas

  • Structural Biology
  • Molecular Biology

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