Nonheme iron-oxo and -superoxo reactivities: O 2 binding and spin inversion probability matter

Abstract

DFT calculated barriers for C-H activation of 1,4-cyclohexadiene by nonheme iron(iv)-oxo and iron(iii)-superoxo species show that the experimental trends can be explained if the spin inversion probability of the TMC iron(iv)-oxo is assumed to be poor. Also, the TMC iron(iii)-superoxo reaction proceeds with an endothermic O 2-binding energy followed by an intrinsically reactive quintet state. © 2012 The Royal Society of Chemistry.