title: An Iron(II)(1,3-bis(2'-pyridylimino)isoindoline) Complex as a Catalyst for Substrate Oxidation with H2O2. Evidence for a Transient Peroxodiiron(III) Species.
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)2in 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 H2O2as the oxidant. Hammett correlations and kinetic isotope effect experiments support the involvement of an electrophilic metal-based oxidant. A metastable green species (2) is observed when1is reacted with H2O2at -40 °C, which has been characterized to have a FeIII(μ-O)(μ-O2)FeIIIcore on the basis of UV-Vis, electron paramagnetic resonance, resonance Raman, and X-ray absorption spectroscopic data.
authors.affiliation: Department of Chemistry, University of Pannonia, 8201 Veszprém, Wartha Vince u. 1., Hungary.
authors.forename: József S
authors.initials: JS
authors.lastname: Pap
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Cranswick
authors.affiliation: Department of Chemistry, University of Pannonia, 8201 Veszprém, Wartha Vince u. 1., Hungary.
authors.forename: E
authors.initials: E
authors.lastname: Balogh-Hergovich
authors.affiliation: Department of Chemistry, University of Pannonia, 8201 Veszprém, Wartha Vince u. 1., Hungary.
authors.forename: Gábor
authors.initials: G
authors.lastname: Baráth
authors.affiliation: Aix-Marseille Université, FR1739, Spectropole, Campus St. Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille cedex 20, France.
authors.forename: Michel
authors.initials: M
authors.lastname: Giorgi
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA.
authors.forename: Gregory T
authors.initials: GT
authors.lastname: Rohde
authors.affiliation: Department of Chemistry, University of Pannonia, 8201 Veszprém, Wartha Vince u. 1., Hungary.
authors.forename: József
authors.initials: J
authors.lastname: Kaizer
authors.affiliation: Department of Chemistry, University of Pannonia, 8201 Veszprém, Wartha Vince u. 1., Hungary.
authors.forename: Gábor
authors.initials: G
authors.lastname: Speier
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA.
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
keywords: Catalytic oxidation; Iron-peroxo intermediate; Isoindoline; Nonheme iron complex; Tridentate ligand