Identification of High-Valent Fluoroiron Porphyrin Intermediates Associated with the Electrocatalytic Functionalization of Hydrocarbons

Article abstract of DOI:10.1021/ja00227a019

The difluoroiron(III) tetraphenylporphyrin complex undergoes a one-electron oxidation at 0.68 V (SCE) in contrast with values of 1.1 V measured for the monofluoroiron(III) porphyrin and the other five-coordinate iron(III) porphyrin complexes.Cyclic voltammetric oxidation of the difluoroiron(III) species in dichloromethane solution is quasi-reversible as a consequence of an EC mechanism.Reversible waves are favored at high scan rates and lower temperatures.Increased water content serves to make the oxidative cyclic voltammetric process irreversible presumably due to a disproportionation process.In the presence of added olefin substrates, this EC process permits efficient electrocatalytic oxidation to the epoxide, allylic alcohol, and enone.Tertiary carbon units are converted to the corresponding alcohol.Utilization of fluoride ion permits generation and low-temperature spectroscopic identification of a highly oxidized iron porphyrin species.The high-valent complex is produced at -78 deg C through addition of m-chloroperbenzoic acid to monofluoroiron(III) tetraarylporphyrins or by fluoride ion promoted disproportionation of the dication radical μ-oxo dimeric iron(III) porphyrin derivative.The oxidized iron porphyrin species is competent to effect olefin epoxidation at -78 deg C.Low-temperature 1H and 2H NMR spectroscopies demonstrate the porphyrin ?-cation radical nature of the high-valent species, in that porphyrin phenyl resonances are drastically shifted in alternating upfield and downfield directions.The electron spin resonance spectrum is consistent with an S = 3/2 ground state, and the high-valent intermediate is assigned a tentative fluorooxoiron(IV) porphyrin ?-cation radical formulation.