Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme Fe-III-OOH and Fe-III-O-Fe-III Complexes at Room Temperature

The formation of an Fe-III-OOH species by reaction of complex 1 ([(MeN3Py)Fe-II(CH3CN)(2)](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe-III-OOH species, and its subsequent conversion to relatively inert Fe-III-O-Fe-III species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the Fe-III-OOH species formed