The active oxidant that oxygenates organic substrates is an iron(IV) oxo intermediate, namely, [(tpa)FeIV(O)(CH3CN)]2+ (2), which is formed through OO 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.
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