Mechanism of four-electron reduction of dioxygen to water by ferrocene derivatives in the presence of perchloric acid in benzonitrile, catalyzed by cofacial dicobalt porphyrins.

摘要: The selective two-electron reduction of dioxygen occurs in the case a monocobalt porphyrin [Co(OEP)], whereas four-electron cofacial dicobalt [Co2(DPX)]. other porphyrins [Co2(DPA), Co2(DPB), and Co2(DPD)] also catalyze dioxygen, but is not as efficient Co2(DPX). μ-superoxo species were produced by reactions dicobalt(II) with presence bulky base subsequent one-electron oxidation resulting μ-peroxo iodine. superhyperfine structure due to two equivalent cobalt nuclei was observed at room temperature ESR spectra species. coupling constant Co2(DPX) largest among those porphyrins. This indicates that catalysis Co2(...