Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2013, Issue 22-23, Pages 3858-3866Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201300162
Keywords
Iron; Tridentate ligands; N ligands; Peroxido ligands; Oxidation
Categories
Funding
- Hungarian Academy of Sciences
- Hungarian Government
- European Union
- European Social Fund [TAMOP-4.2.2.A-11/1/KONV-2012-0071]
- U.S. National Institutes of Health (NIH) [GM-38767, ES017390]
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Center for Research Resources, Biomedical Technology Program [P41RR001209]
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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 degrees C and has a Fe-III(-O)(-O-2)Fe-III core on the basis of UV/Vis, electron paramagnetic resonance, resonance Raman, and X-ray absorption spectroscopic data.
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