Hidden radical reactivity of the [FeO]2+ group of the (hydro)oxide species in the H-abstraction from methane: a DFT and CASPT2 study

TL;DR

This study investigates the radical reactivity of the [FeO]2+ group in methane H-abstraction, revealing the role of the metastable oxyl state FeIII-O* through DFT and CASPT2 calculations.

Contribution

It provides new insights into the radical reactivity mechanism of the [FeO]2+ group in methane activation using advanced quantum-chemical methods.

Findings

Metastable oxyl state FeIII-O* causes negative spin polarization in methyl.

Quantum-chemical models show the radical reactivity of [FeO]2+ in methane H-abstraction.

The study highlights the importance of the oxyl state in reactivity mechanisms.

Abstract

Reactivity of the [FeO]2+ group in the abstraction of hydrogen from methane is determined by metastable oxyl state FeIII-O* causing the negative spin polarization of the methyl moiety as was shown by quantum-chemical means with the use of model iron hydroxide species FeO(OH)2, Fe2O(OH)5, and Fe4O5(OH)3 as an example.