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

Shunichi Fukuzumi; Seiii Mochizuki; Toshio Tanaka

doi:10.1021/ic00311a042

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

Shunichi Fukuzumi, Seiii Mochizuki, Toshio Tanaka

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

147 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 language	English
Pages (from-to)	2459-2465
Number of pages	7
Journal	Inorganic Chemistry
Volume	28
Issue number	12
DOIs	https://doi.org/10.1021/ic00311a042
State	Published - 1 Jun 1989

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@article{3e2b093e2c534790866bb20120fbb189,

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

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.",

author = "Shunichi Fukuzumi and Seiii Mochizuki and Toshio Tanaka",

year = "1989",

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doi = "10.1021/ic00311a042",

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T1 - Efficient Reduction of Dioxygen with Ferrocene Derivatives, Catalyzed by Metalloporphyrins in the Presence of Perchloric Acid

AU - Fukuzumi, Shunichi

AU - Mochizuki, Seiii

AU - Tanaka, Toshio

PY - 1989/6/1

Y1 - 1989/6/1

N2 - 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.

AB - 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.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

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

Abstract

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