An Iron(III) Superoxide Corrole from Iron(II) and Dioxygen

Angew Chem Int Ed Engl. 2022 Jan 10;61(2):e202111492. doi: 10.1002/anie.202111492. Epub 2021 Nov 30.

Abstract

A new structurally characterized ferrous corrole [FeII (ttppc)]- (1) binds one equivalent of dioxygen to form [FeIII (O2-. )(ttppc)]- (2). This complex exhibits a 16/18 O2 -isotope sensitive ν(O-O) stretch at 1128 cm-1 concomitantly with a single ν(Fe-O2 ) at 555 cm-1 , indicating it is an η1 -superoxo ("end-on") iron(III) complex. Complex 2 is the first well characterized Fe-O2 corrole, and mediates the following biologically relevant oxidation reactions: dioxygenation of an indole derivative, and H-atom abstraction from an activated O-H bond.

Keywords: dioxygen activation; hydrogen atom transfer; iron; porphyrinoids; superoxide.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Ferric Compounds / chemistry
  • Ferrous Compounds / chemistry
  • Iron / chemistry
  • Molecular Structure
  • Oxidation-Reduction
  • Oxygen* / chemistry
  • Porphyrins* / chemistry
  • Superoxides* / chemistry

Substances

  • Oxygen
  • corrole
  • Superoxides
  • Porphyrins
  • Iron
  • Ferric Compounds
  • Ferrous Compounds