O 2 activation under mild conditions remains a weighty challenge for chemists. Herein we report a study of electrochemical O 2 reductive activation catalyzed by Fe III (F 20 TPP)Cl, by means of cyclic voltammetry and UV−vis spectroelectrochemistry in acidic solutions of N,N-dimethylformamide. Two parallel catalytic pathways have been evidenced occurring at different overpotentials. At high overpotential a classical electron−proton (EPT) pathway where protonation of Fe peroxo ultimately leads to the formation of high-valent Fe oxo species dominates. At low overpotential a proton−electron (PET) pathway involving a hydrosuperoxo species has been identified.solution, and evolution of Fe III OH 2 + and Fe III OO − species of Fe(F 20 TPP) (PDF) AUTHOR INFORMATION
Herein we report the first example of using scanning electrochemical microscopy (SECM) to quantitatively analyze O2 reductive activation in organic media catalyzed by three different Fe porphyrins. For each porphyrin, SECM can provide in one single experiment the redox potential of various intermediates, the association constant of FeII with O2, and the pKa of the FeIII(OOH−)/ FeIII(OO2−) couple. The results obtained can contribute to a further understanding of the parameters controlling the catalytic efficiency of the Fe porphyrin towards O2 activation and reduction.
Herein we report the first example of using scanning electrochemical microscopy (SECM) to quantitatively analyze O2 reductive activation in organic media catalyzed by three different Fe porphyrins. For each porphyrin, SECM can provide in one single experiment the redox potential of various intermediates, the association constant of FeII with O2, and the pKa of the FeIII(OOH−)/ FeIII(OO2−) couple. The results obtained can contribute to a further understanding of the parameters controlling the catalytic efficiency of the Fe porphyrin towards O2 activation and reduction.
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