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-cydohexanediamine) 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. [ABSTRACT FROM AUTHOR]