title: Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants.
abstract: The study of C-H bond activation reactions by nonheme Fe(IV)O 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 KIE(exp) 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.
authors.affiliation: Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem , 91904 Jerusalem, Israel.
authors.forename: Debasish
authors.initials: D
authors.lastname: Mandal
authors.affiliation: Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem , 91904 Jerusalem, Israel.
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik