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.
Department of Chemistry and Biochemistry, Auburn University , Auburn, Alabama 36849, United States.
Qiao
Q
Zhang
Christian R
CR
Goldsmith