An iron(II)[1,3-bis(2'-pyridylimino)isoindoline] complex as a catalyst for substrate oxidation with H2O2 - Evidence for a transient peroxidodiiron(III) species

József S. Pap, Matthew A. Cranswick, É Balogh-Hergovich, Gábor Baráth, Michel Giorgi, Gregory T. Rohde, József Kaizer, Gábor Speier, Larry Que

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Abstract

The complex [Fe(indH)(solvent)3](ClO4)2 (1) has been isolated from the reaction of equimolar amounts of 1,3-bis(2'-pyridylimino)isoindoline (indH) and Fe(ClO4)2 in acetonitrile and characterized by X-ray crystallography and several spectroscopic techniques. It is a suitable catalyst for the oxidation of thioanisoles and benzyl alcohols with H2O2 as the oxidant. Hammett correlations and kinetic isotope effect experiments support the involvement of an electrophilic metalbased oxidant. A metastable green species (2) is observed when 1 is reacted with H2O2 at -40 °C and has a FeIII(μ-O)(μ-O2)FeIII core on the basis of UV/Vis, electron paramagnetic resonance, resonance Raman, and X-ray absorption spectroscopic data.

Original languageEnglish (US)
Pages (from-to)3858-3866
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number22-23
DOIs
StatePublished - Oct 31 2013

Keywords

  • Iron
  • N ligands
  • Oxidation
  • Peroxido ligands
  • Tridentate ligands

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