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An Iron(II)[1,3‐bis(2′‐pyridylimino)isoindoline] Complex as a Catalyst for Substrate Oxidation with H 2 O 2 – Evidence for a Transient Peroxidodiiron(III) Species
Author(s) -
Pap József S.,
Cranswick Matthew A.,
BaloghHergovich É.,
Baráth Gábor,
Giorgi Michel,
Rohde Gregory T.,
Kaizer József,
Speier Gábor,
Que Lawrence
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300162
Subject(s) - chemistry , isoindoline , acetonitrile , catalysis , electron paramagnetic resonance , redox , substrate (aquarium) , kinetic isotope effect , inorganic chemistry , resonance (particle physics) , metal , photochemistry , medicinal chemistry , deuterium , organic chemistry , nuclear magnetic resonance , physics , oceanography , quantum mechanics , geology , particle physics
The complex [Fe(indH)(solvent) 3 ](ClO 4 ) 2 ( 1 ) has been isolated from the reaction of equimolar amounts of 1,3‐bis(2′‐pyridylimino)isoindoline (indH) and Fe(ClO 4 ) 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 H 2 O 2 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 H 2 O 2 at –40 °C and has a Fe III (μ‐O)(μ‐O 2 )Fe III core on the basis of UV/Vis, electron paramagnetic resonance, resonance Raman, and X‐ray absorption spectroscopic data.