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• W2037936475 abstract "We have studied the intermediates generated by the oxidation of the bromo[5-o-nitrophenyl,10,15,20- triphenylporphyrin)iron(III)] complex with iodosylbenzene in dichloromethane. We previously observed that the oxidation of cyclohexane with this system gave a 60% yield of cyclohexanol based on iodosylbenzene. The intermediate species were studied by visible spectra at −60 °C and at room temperature, and also by electron paramagnetic resonance (EPR). The electronic spectra, after reaction occurred between 0–15 s, indicate the formation of a Fe(IV) species and dimeric species; at 10–15 s a green solution was also obtained. The EPR spectra in the same conditions exhibit a signal at g=2.0016, assigned to a radical. These results gave rise to the conclusion that the catalytic species in this system is the dimeric ferryl porphyrin π-cation radical, (P)FeIV-O-FeIV(O)(P·+) (P is the porphyrin). Through the dimer formation the orthogonality of the ferryl-iron is retained (D4h symmetry) preventing magnetic coupling with the porphyrinic ring radical. Thus, this radical is observed by EPR. These results do not exclude the possibility of the existence of a monomeric ferryl porphyrin π-cation radical as the catalytic species." @default.
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• W2037936475 date "1991-09-01" @default.
• W2037936475 modified "2023-10-16" @default.
• W2037936475 title "An EPR and electronic spectroscopy study of intermediates in a mono o-nitro substituted iron porphyrin reaction with iodosylbenzene" @default.
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• W2037936475 doi "https://doi.org/10.1016/s0020-1693(00)82983-7" @default.
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