Directing a Non-Heme Iron(III)-Hydroperoxide Species on a Trifurcated Reactivity Pathway

The reactivity of [Fe-III(tpena)](2+) (tpena=N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N-acetate) as a catalyst for oxidation reactions depends on its ratio to the terminal oxidant H2O2 and presence or absence of sacrificial substrates. The outcome can be switched between: 1)catalysed H2O2 disproportionation, 2)selective catalytic oxidation of methanol or benzyl alcohol to the corresponding aldehyde, or 3)oxidative decomposition of the tpena ligand. A common mechanism is proposed involving homolytic O-O cleavage in the detected transient purple low-spin (S=1/2) [(tpenaH)(FeO)-O-III-OH](2+). The resultant iron(IV) oxo and hydroxyl radical both participate in controllable hydrogen-atom transfer (HAT) reactions. Consistent with the presence of a weaker sigma-donor carboxylate ligand, the most pronounced difference in the spectroscopic properties of [Fe(OOH)(tpenaH)](2+) and its conjugate base, [Fe(OO)(tpenaH)](+), compared to non-heme iron(III) peroxide analogues supported by neutral multidentate N-only ligands, are slightly blue-shifted maxima of the visible absorption band assigned to ligand-to-metal charge-transfer (LMCT) transitions and, corroborating this, lower Fe-III/Fe-II redox potentials for the pro-catalysts.