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Experimental and Theoretical Evidence for Nonheme Iron(III) Alkylperoxo Species as Sluggish Oxidants in Oxygenation Reactions


  • This research was supported by KOSEF/MOST through Creative Research Initiative Program (W.N.), Grants-in-Aid (No. 18350088, 18GS02070005, and 18066013) for Scientific Research from JSPS (K.Y.), the Nanotechnology Support Project of MEXT (K.Y.), the Joint Project of Chemical Synthesis Core Research Institutions of MEXT (K.Y.), CREST of Japan Science and Technology Cooperation (K.Y.), a Grant-in-Aid (No. 18750048) for Young Scientists from JSPS (T.K.), and the AmorePacific R&D Center (M.J.P.).


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The active oxidant that oxygenates organic substrates is an iron(IV) oxo intermediate, namely, [(tpa)FeIV(O)(CH3CN)]2+ (2), which is formed through O[BOND]O bond homolysis, according to experimental and computational studies on the reactivity of nonheme iron(III) alkylperoxo complex [(tpa)FeIII(OOtBu)(CH3CN)]2+ (1), which was shown to be a sluggish electrophilic oxidant that is incapable of oxygenating organic substrates. tpa=tris(2-pyridylmethyl)amine.