Electron Configuration of the [FeO](2+) Group in the H-Abstraction from Methane: Oxyl versus Ferryl
arXiv.org, e-Print Archive, Condensed Matter
Zilberberg Igor L.
Boreskov Institute of Catalysis, Novosibirsk 630090, Russian Federation
This account presents author's opinion on the mechanism of the H-abstraction from methane by the [FeO](2+) group. In the course of reaction with hydrogen, the Fe-O bond in the ferryl configuration becomes elongated causing transfer of the spin-up electron from one of doubly occupied bonding orbitals leaving behind single spin-down electron on oxygen. This oxygen in so-formed oxyl configuration of the [FeO](2+) moiety then easily accept the spin-up hydrogen atom from methane in the same way as the radical-localized oxygen does. This mechanism is compared with the scheme in which the hydrogen is accepted by low-lying unoccupied antibonding orbital in the ferryl configuration.