fulltext.study @t Gmail

EPR detection of Fe(V)=O active species in nonheme iron-catalyzed oxidations

Paper ID Volume ID Publish Year Pages File Format Full-Text
49845 46769 2012 4 PDF Available
Title
EPR detection of Fe(V)=O active species in nonheme iron-catalyzed oxidations
Abstract

Very recently, in situ cryospray-assisted variable temperature mass spectrometry (VT-MS) has been used to obtain the first convincing evidence for a HO–FeV=O intermediate in the catalyst system [(Me2PyTACN)FeII(OTf)2] (4)/H2O2 (Me2PyTACN = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, OTf = OSO2CF3). The herein presented EPR spectroscopic study of the same system witnesses the formation of S = 1/2 reactive iron species. Its EPR parameters, in combination with its reactivity pattern toward cyclohexene and with independently obtained VT-MS data, allow for its reasonable assignment to the reactive [(Me2PyTACN)FeV=O(OH)]2 + (4c) species.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► High-valent intermediate of nonheme Fe/H2O2 catalyst system shows rhombic EPR signal. ► This intermediate is active toward cyclohexene oxidation. ► Based on EPR and MS data the active intermediate is assigned to a FeV = O species.

Keywords
Bioinorganic chemistry; EPR; Hydrogen peroxide; Iron; Oxidation; Reaction mechanisms
First Page Preview
EPR detection of Fe(V)=O active species in nonheme iron-catalyzed oxidations
Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Communications - Volume 29, 5 December 2012, Pages 105–108
Authors
, , , , ,
Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis