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.

Significant Solvent Effect on Reactivity of Oxoiron(IV) Porphyrin π-Cation Radical Complex: Activation in n-Alkane Solvent.

The solvent effect on the reactivity of high-valent metal oxo complexes has not been studied well, because of their solubility and stability. We synthesize oxoiron(IV) porphyrin π-cation radical complexes (1-CompI and 2-CompI) having the n-hexyl side chains. 1-CompI and 2-CompI are soluble in various solvents, even in hexane, at -80 °C, allowing for the study of their reactivity in various organic solvents. We show that pentane, hexane, heptane, and tert-butyl methyl ether significantly increase the reactivity of 1-CompI and 2-CompI, but dichloromethane, the most frequently used solvent in previous studies, is the worst for increasing the reactivity among the solvents. 1H NMR and EPR spectroscopies show no significant change in hexane, but the Eyring plots for the epoxidation reactions indicate that the entropies of activation in n-alkane solvents are larger than those in dichloromethane. The observed solvent effect can be rationalized with reorganization energy of the solvent in the reaction.

Experimental and theoretical studies of the porphyrin ligand effect on the electronic structure and reactivity of oxoiron(iv) porphyrin π-cation-radical complexes.

Oxoiron(IV) porphyrin π-cation-radical complexes (Cpd I) have been studied as models for reactive intermediates called compound I in cytochromes P450, peroxidases, and catalases. It has been well known that the electronic structure and reactivity of Cpd I are modulated by the substituted position and the electron-withdrawing ability of the substituent. However, there still remain two major questions: (1) how many electronegative halogen atoms should be introduced in the meso-phenyl group to switch the porphyrin π-cation-radical state of Cpd I? (2) How does the electron-withdrawing effect of the substituent modulate the reactivity of Cpd I? To answer these two questions, we here performed experimental and theoretical studies on the electron-withdrawing effect of the meso-substituent. We gradually increased the electron-withdrawing effect by increasing the number of fluorine atoms in the meso-phenyl group. Spectroscopic analyses of these Cpd I models reveal that the porphyrin radical state shifts from having a2u radical character to having a1u radical character with an increase in the number of the fluorine atoms in the phenyl group, and the ground state of Cpd I switches from the a2u state to the a1u state when four fluorine atoms are introduced in the meso-phenyl group. The switch of the radical state is predicted well by LC-BLYP, but not by the commonly used B3LYP. The theoretical calculations indicate that the electron-withdrawing substituent makes Cpd I more reactive by stabilizing the ferric porphyrin state (product state) more than the Cpd I state (reactant state), generating a larger free energy change in the oxygenation reaction (ΔG) of Cpd I.

Direct Observation of Primary C-H Bond Oxidation by an Oxido-Iron(IV) Porphyrin π-Radical Cation Complex in a Fluorinated Carbon Solvent.

Oxido-iron(IV) porphyrin π-radical cation species are involved in a variety of heme-containing enzymes and have characteristic oxidation states consisting of a high-valent iron center and a π-conjugated macrocyclic ligand. However, the short lifetime of the complex has hampered detailed reactivity studies. Reported herein is a remarkable increase in the lifetime (80 s at 10 °C) of FeIV (TMP+. )(O)(Cl) (2; TMP=5,10,15,20-tetramesitylporphyrin dianion), produced by the oxidation of FeIII (TMP)(Cl) (1) by ozone in α,α,α-trifluorotoluene (TFT). The lifetime is 720 times longer compared to that of the currently most stable species reported to date. The increase in the lifetime improves the reaction efficiency of 2 toward inert alkane substrates, and allowed observation of the reaction of 2 with a primary C-H bond (BDEC-H =ca. 100 kcal mol-1 ) directly. Activation parameters for cyclohexane hydroxylation were also obtained.