Revealing the Structure and Reactivity of the Active Species in the FeCl₂–TBHP System: Case Study on Alkene Oxidation

A mechanism involving a quintet ferryl [Fe^IVO] species has been disclosed for the oxidation of alkene under the FeCl₂–TBHP system. Both theoretical and experimental results suggested that the quintet ferryl species [Fe^IVO] was produced by the reaction of FeCl₂ with TBHP. A Mulliken atomic spin density distribution on [Fe^IVO] showed that the O site has strong radical character and could easily react with alkene to form a carbon radical intermediate. This radical could be further oxidized by TBHP to lead to the CC bond cleavage of alkene.