Catalytic H2O2 Activation by a Diiron Complex for Methanol Oxidation.

In nature, C-H bond oxidation of CH4 involves a peroxo intermediate that decays to the high-valent active species of either a "closed" {FeIV(μ-O)2FeIV} core or an "open" {FeIV(O)(μ-O)FeIV(O)} core. To mimic and to obtain more mechanistic insight in this reaction mode, we have investigated the reactivity of the bioinspired diiron complex [(susan){Fe(OH)(μ-O)Fe(OH)}]2+ [susan = 4,7-dimethyl-1,1,10,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazadecane], which catalyzes CH3OH oxidation with H2O2 to HCHO and HCO2H. The kinetics is faster in the presence of a proton. 18O-labeling experiments show that the active species, generated by a decay of the initially formed peroxo intermediate [(susan){FeIII(μ-O)(μ-O2)FeIII}]2+, contains one reactive oxygen atom from the μ-oxo and another from the μ-peroxo bridge of its peroxo precursor. Considering an FeIVFeIV active species, a "closed" {FeIV(μ-O)2FeIV} core explains the observed labeling results, while a scrambling of the terminal and bridging oxo ligands is required to account for an "open" {FeIV(O)(μ-O)FeIV(O)} core.