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

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Lyakin, Oleg Y.
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Prat Casellas, Irene
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Bryliakov, Konstantin P.
orcId Costas Salgueiro, Miquel​ researcherId Costas Salgueiro, Miquel​ scopusId Costas Salgueiro, Miquel​ ​
Costas Salgueiro, Miquel
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Talsi, Evgenii P.
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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 ​
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