Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts

Angew Chem Int Ed Engl. 2017 Apr 18;56(17):4772-4776. doi: 10.1002/anie.201701319. Epub 2017 Mar 24.

Abstract

We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn(s PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2 FeII MnII vs. FeIII3 MnII ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

Keywords: C−H bond oxygenation; clusters; iodosobenzene adduct; multimetallic complexes; oxygen atom transfer.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Crystallography, X-Ray
  • Electrons
  • Iodobenzenes / chemistry*
  • Iron Compounds / chemistry*
  • Manganese / chemistry*
  • Models, Molecular
  • Oxidation-Reduction
  • Oxygen / chemistry*

Substances

  • Iodobenzenes
  • Iron Compounds
  • Manganese
  • Oxygen
  • iodosobenzene