The oxidation of cyclo-olefin by the S = 2 ground-state complex [Fe^IV(O)(TQA)(NCMe)]²

Density functional theory calculation is used to investigate the oxidation of cyclo-olefin (cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclo-octene) by the complex [Fe^IV(O)(TQA)(NCMe)]²⁺, which has S = 2 ground state, and the effect of electronic factors and steric hindrance on reaction barriers. Our results suggest that the oxo-iron(IV) complex can oxidise C-H and C = C bonds via a single-state mechanism, and two different ways of electron transport exist. The energy barriers initially decrease with increasing substrate size, and the trend then reverses. Comparison of the energy barrier in different systems reveals that except for the reaction between [Fe^IV(O)(TQA)(NCMe)]²⁺ and cycloheptene, oxo-iron(IV) complexes prefer epoxidation to hydroxylation. However, the hydroxylated product is more stable than the corresponding epoxidated product. This result indicates that the products of epoxidation tend to decompose first. The energy barrier of hydroxylation and epoxidation originates from the balance of orbital interaction and Pauli repulsion from the equatorial ligand and protons on the approaching substrate. In this regard, we calculate the weak interaction between two fragments (oxo-iron complex and substrates) using the independent gradient model and drawn the corresponding 3D isosurface representations of reactants.