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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)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 metal-based oxidant. A metastable green species (2) is observed when 1 is reacted with H2O2 at -40 °C, which has been characterized to have a FeIII(?-O)(?-O2)FeIII core on the basis of UV-Vis, electron paramagnetic resonance, resonance Raman, and X-ray absorption spectroscopic data.

SUBMITTER: Pap JS 

PROVIDER: S-EPMC3935335 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature

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An Iron(II)(1,3-bis(2'-pyridylimino)isoindoline) Complex as a Catalyst for Substrate Oxidation with H<sub>2</sub>O<sub>2</sub>. Evidence for a Transient Peroxodiiron(III) Species.

Pap József S JS   Cranswick Matthew A MA   Balogh-Hergovich E E   Baráth Gábor G   Giorgi Michel M   Rohde Gregory T GT   Kaizer József J   Speier Gábor G   Que Lawrence L  

European journal of inorganic chemistry 20130801 22-23

The complex [Fe(indH)(solvent)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> (<b>1</b>) has been isolated from the reaction of equimolar amounts of 1,3-bis(2'-pyridylimino)isoindoline (indH) and Fe(ClO<sub>4</sub>)<sub>2</sub> 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 H<sub>2</sub>O<sub>2</sub> as the oxidant. Hammett correlations and kinetic isotope effect expe  ...[more]

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