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.