title: Effect of external electric fields on the C-H bond activation reactivity of nonheme iron-oxo reagents.
abstract: The effect of external electric fields (EFs) on the reactivity of nonheme iron(IV)-oxo species toward alkanes is investigated computationally using density functional theory. It is shown that an external EF changes the energy landscape of the process and thereby impacts the mechanisms, rates, and selectivities of the reactions, in a manner dependent on the nature of the iron(IV)-oxo/alkane pair. When the iron-oxo species is a good electron acceptor, like N4PyFeO2+, and the alkane is a good electron donor, like toluene, the application of the EF changes the mechanism from hydrogen abstraction to electron transfer. With cyclohexane, which is a poorer electron donor than toluene, the EF promotes hydride transfer and generates a carbocation. However, in the reaction between a poorer electron acceptor TMC(SR)FeO+ and cyclohexane, the EF preserves the hydrogen abstraction/rebound mechanism but improves its features by lowering the barriers for both the C-H activation and rebound steps; larger effects were observed for the quintet-state reaction. In all cases, the EF effect obeys a selection rule; the largest effects are observed when the EF vector is aligned with the Fe=O axis (z) and directed along the molecular dipole. As such, an EF aligned in the direction of the electron flow from substrate to the iron-oxo center lowers the reaction barrier and affects both the reactivity and selectivity of the molecular catalysts.
authors.affiliation: The Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel.
authors.forename: Hajime
authors.initials: H
authors.lastname: Hirao
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.forename: Maria Angels
authors.initials: MA
authors.lastname: Carvajal
authors.forename: Yong
authors.initials: Y
authors.lastname: Wang
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik