Kinetic Analysis of the Formation and Decay of a Non-Heme Ferric Hydroperoxide Species Susceptible to O–O Bond Homolysis

The formation of a ferric hydroperoxide species from [Fe­(bbpc)­(MeCN)2]2+ (bbpc = N,N′-dibenzyl-N,N′-bis­(2-pyridylmethyl)-1,2-cyclohexanediamine) and its subsequent decomposition were analyzed kinetically. The rate of decay is not strongly influenced by the presence of either water or substrate, suggesting that the ferric hydroperoxide degrades through O–O bond homolysis and is not the relevant metal-based oxidant in the observed catalysis of C–H activation. The rate law corresponding to the complex’s formation from O2 is consistent with the intermediacy of a mononuclear ferric superoxo species.