The C-H bond activation by non-heme oxidant [(N4Py)FeIV(O)]2+ with external electric field

The C-H bond activation by non-heme iron-oxo species is one of the most interesting fundamental steps in organic oxidation reactions. This work focuses on the C-H bond activation by an external electric field (EEF) in a non-heme complex. The hydrogen atom abstraction from 2,5-(MeO)(2)C6H3CH2OH by [(N4Py)Fe-IV(O)](2+) utilizing an EEF was studied using density functional theory. Our analysis suggests that the mechanism of this process can be characterized as a mixture of hydrogen atom transfer and concerted-asynchronous electron-proton transfer that can be modulated by the EEF. Our study demonstrates an EEF that decreases the reaction barrier by increasing the electron donor orbital energy, which facilitates electron transfer. The reaction finally becomes barrierless when the EEF is greater than 0.0045au. The finding from this work demonstrates the exciting possibility of tuning the reaction mechanism using the EEF.