Ligand field effects on the ground and excited states of reactive FeO2+ species.

摘要: High-valent Fe(iv)-oxo species have been found to be key oxidizing intermediates in the mechanisms of mononuclear iron heme and non-heme enzymes that can functionalize strong C-H bonds. Biomimetic molecular complexes successfully synthesized characterized, but their catalytic reactivity is typically lower than enzymatic analogues. The activation step proceeds through two competitive mechanisms, named σ- π-channels. We performed high-level wave function theory calculations on bare FeO2+ a series model order elucidate electronic properties ligand field effects those channels. Our results suggest coordination environment formed by weak gives access both channels, yielding more reactive sites. In contrast, stabilizes only σ-channel. concluding remarks will aid derivation new structure-reactivity descriptors contribute development next generation functional catalysts.