Rate-Limiting Step of Epoxidation Reaction of the Oxoiron(IV) Porphyrin π-Cation Radical Complex: Electron Transfer Coupled Bond Formation Mechanism.

Epoxidation reactions catalyzed by high-valent metal-oxo species are key reactions in various biological and chemical processes. Because the redox potentials of alkenes are higher than those of most high-valent metal-oxo species, the electron transfer (ET) from the alkene to the high-valent metal-oxo species in the epoxidation reaction is endergonic and must be coupled with another exergonic process. To reveal the mechanism of the ET, we performed a Marcus plot analysis for the epoxidation reaction of the oxoiron(IV) porphyrin π-cation radical complex (compound I) with alkene. The Marcus plots can be simulated with a linear line with the gradient of 0.50 when the redox potential of compound I varies and 0.07 when the redox potential of alkene varies. These results indicate that the ET process is involved in the rate-limiting step and coupled with the following O-C bond formation process: ET coupled bond formation mechanism. The DFT calculations support this conclusion and disclose the details of the mechanism. As the alkene comes close to the oxo ligand, the energy of the highest occupied molecular orbital (HOMO) of the alkene increases and the energy for the ET becomes small enough to allow the ET. Finally, the ET occurs from the HOMO of the alkene to the porphyrin π-radical orbital. The shift of one electron from the HOMO of the alkene by the ET simultaneously results in the O-C half bond formation between the oxo ligand and the alkene. The ET process itself is still endergonic and reversible, but the bond formation coupled with the ET changes the overall process to exergonic and irreversible. We also discuss the similarity with the aromatic hydroxylation reaction and the relevance to the epoxidation reactions of other metal-oxo complexes and peracid.