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

Very recently, in situ cryospray-assisted variable temperature mass spectrometry (VT-MS) has been used to obtain the first convincing evidence for a HO-Fe-V=O intermediate in the catalyst system [((Me2)PyTACN) Fe-II(OTf)(2)] (4)/H2O2 ((Me2)PyTACN = 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 [((Me2)PyTACN)Fe-V=O(OH)](2+) (4c) species

The authors thank the Russian Foundation for Basic Research, grants 12-03-31709 and 12-03-00782, for financial support. M.C. thanks MCYT (CTQ-2009-08864, and Consolider Ingenio CSD-2010-00065), ERC-2009-StG-239910, ICREA Academia Awards and SGR-239910

Elsevier

Manager: Ministerio de Ciencia e Innovación (Espanya)
Ministerio de Ciencia y Tecnología (Espanya)
Author: Lyakin, Oleg Y.
Prat Casellas, Irene
Bryliakov, Konstantin P.
Costas Salgueiro, Miquel
Talsi, Evgenii P.
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-Fe-V=O intermediate in the catalyst system [((Me2)PyTACN) Fe-II(OTf)(2)] (4)/H2O2 ((Me2)PyTACN = 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 [((Me2)PyTACN)Fe-V=O(OH)](2+) (4c) species
The authors thank the Russian Foundation for Basic Research, grants 12-03-31709 and 12-03-00782, for financial support. M.C. thanks MCYT (CTQ-2009-08864, and Consolider Ingenio CSD-2010-00065), ERC-2009-StG-239910, ICREA Academia Awards and SGR-239910
Document access: http://hdl.handle.net/2072/295530
Language: eng
Publisher: Elsevier
Rights: Tots els drets reservats
Subject: Química bioinorgànica
Bioinorganic chemistry
Aigua oxigenada
Hydrogen peroxide
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Peròxids -- Oxidació
Peroxides -- Oxidation
Title: EPR detection of Fe(V)=O active species in nonheme iron-catalyzed oxidations
Type: info:eu-repo/semantics/article
Repository: Recercat

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