Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants

The study of C-H bond activation reactions by nonheme (FeO)-O-IV species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.