Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex.

Thomas M PangiaCasey G DaviesJoshua R PrendergastJesse B GordonMaxime A SieglerGuy N L Jameson David P Goldberg

Published in: Journal of the American Chemical Society (2018)

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.

Keyphrases

iron deficiency
high resolution
solid state
electron transfer
transition metal