Efficient Reduction of Dioxygen with Ferrocene Derivatives, Catalyzed by Metalloporphyrins in the Presence of Perchloric Acid

Shunichi Fukuzumi, Seiii Mochizuki, Toshio Tanaka

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146 Scopus citations

Abstract

Reduction of dioxygen with ferrocene derivatives (Fc) is catalyzed by metalloporphyrins (MTPP+: M = Co, Fe, Mn; TPP = tetraphenylporphyrin) or Co(TIM)3+(TIM: a tetraaza macrocyclic ligand) in the presence of HC104 in acetonitrile (MeCN). Electron transfer from Fc to MTPP+ is the rate-determining step for the MTPP+-catalyzed oxidation of Fc by dioxygen, when the rate is independent of the concentration of dioxygen or HC1O4, On the other hand, the rate of electron transfer from Fc to Co(TIM)3+ is accelerated by the presence of HC104 and dioxygen. The rates of these electron-transfer reactions are discussed in light of the Marcus theory of electron transfer to distinguish between outer-sphere and inner-sphere electron-transfer processes. The strong inner-sphere nature of metalloporphyrins in the electron-transfer reactions with dioxygen in the presence of HC104 plays an essential role in the catalytic reduction of dioxygen.

Original languageEnglish
Pages (from-to)2459-2465
Number of pages7
JournalInorganic Chemistry
Volume28
Issue number12
DOIs
StatePublished - 1 Jun 1989

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