The iron(II) complex with the ligand N,N'-di(benzyl)-N,N'-bis(2-pyridylmethyl)-1,2-cyclohexanediamine (bbpc) can catalyze the oxidation of hydrocarbon C-H bonds by either H2O2 or O2. The architecture of the ligand directs the catalyzed oxidation towards less sterically congested bonds when H2O2 is the terminal oxidant. In both the O2 and H2O2 reactions, an iron(III) hydroperoxide intermediate was characterized. The intermediate's formation from H2O2 and its subsequent decay were studied kinetically with stopped-flow techniques. The inability of protic additives to accelerate the rate of decay suggests that the intermediate's O-O bond cleaves homolytically rather than heterolytically. The rate of decay is independent of the concentration of hydrocarbon substrate, suggesting that the Fe(III)-OOH species is not directly oxidizing the substrate.

Kinetic analysis of the formation and decay of a ferric hydroperoxide complex suggests that it decomposes through O-O bond homolysis and is not directly involved in C-H activation

248th National Meeting (2014)

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