Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex

A nonheme iron­(III) terminal methoxide complex, [FeIII(N3PyO2Ph)­(OCH3)]­ClO4, was synthesized. Reaction of this complex with the triphenylmethyl radical (Ph3C•) leads to formation of Ph3COCH3 and the one-electron-reduced iron­(II) center, as seen by UV–vis, EPR, 1H NMR, and Mössbauer spectroscopy. These results indicate that homolytic Fe–O bond cleavage occurs together with C–O bond formation, providing a direct observation of the “radical rebound” process proposed for both biological and synthetic nonheme iron centers.