Directing a Non-Heme Iron(III)-Hydroperoxide Species on a Trifurcated Reactivity Pathway

Christina Wegeberg, Frants Roager Lauritsen, Cathrine Frandsen, Steen Mørup, Wesley R. Browne, Christine McKenzie*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review


The reactivity of [Fe III(tpena)] 2+ (tpena=N,N,N′-tris(2-pyridylmethyl)ethylenediamine-N′-acetate) as a catalyst for oxidation reactions depends on its ratio to the terminal oxidant H 2O 2 and presence or absence of sacrificial substrates. The outcome can be switched between: 1) catalysed H 2O 2 disproportionation, 2) selective catalytic oxidation of methanol or benzyl alcohol to the corresponding aldehyde, or 3) oxidative decomposition of the tpena ligand. A common mechanism is proposed involving homolytic O−O cleavage in the detected transient purple low-spin (S=1/2) [(tpenaH)Fe IIIO−OH] 2+. The resultant iron(IV) oxo and hydroxyl radical both participate in controllable hydrogen-atom transfer (HAT) reactions. Consistent with the presence of a weaker σ-donor carboxylate ligand, the most pronounced difference in the spectroscopic properties of [Fe(OOH)(tpenaH)] 2+ and its conjugate base, [Fe(OO)(tpenaH)] +, compared to non-heme iron(III) peroxide analogues supported by neutral multidentate N-only ligands, are slightly blue-shifted maxima of the visible absorption band assigned to ligand-to-metal charge-transfer (LMCT) transitions and, corroborating this, lower Fe III/Fe II redox potentials for the pro-catalysts.

Original languageEnglish
JournalChemistry - A European Journal
Issue number20
Pages (from-to)5134-5145
Publication statusPublished - 2018


  • H O activation
  • N,O ligands
  • high-valent iron
  • hydroxyl radical
  • iron(IV)
  • peroxides


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