Iron-oxidation-state-dependent O-O bond cleavage of meta-chloroperbenzoic acid to form an iron(IV)-oxo complex |
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Authors: | Ray Kallol Lee Sang Mok Que Lawrence |
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Institution: | Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA |
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Abstract: | The mechanism of formation of FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at −30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv. peracid and takes place in two successive one-electron steps via an FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv. peracid and produces 0.5 equiv. 3-chlorobenzoic acid, while the second step uses 1 equiv. peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state. |
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Keywords: | Oxoiron(IV) complexes Non-heme ligands O-O bond lysis Iron oxidation state |
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