Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase

研究成果: ジャーナルへの寄稿記事

54 引用 (Scopus)

抄録

A new concerted mechanism is proposed for the conversion of methane to methanol on intermediate Q of soluble methane monooxygenase (sMMO), the active site of which is considered to involve an Fe2(μ-O)2 diamond core. A hybrid density functional theory (DFT) method is used for our mechanistic study on the important reactivity of the bare FeO+ complex and a diiron model of intermediate Q. The reaction pathway for the methane hydroxylation on the diiron complex is essentially identical to that for the gas-phase reaction by the bare FeO+ complex. Methane is highly activated on the dinuclear iron model through the formation of a methane complex, in which a coordinatively unsaturated iron plays a central role in the bonding interaction between the diiron model and substrate methane. A H atom abstraction via a four-centered transition state and a recombination of the OH and CH3 groups via a three-centered transition state successively occur on the dinuclear iron-oxo species, leading to the formation of a methanol complex that corresponds to intermediate T. These electronic processes take place in a concerted manner. Our mechanism for methane hydroxylation by sMMO is different from the radical mechanism that has been widely accepted for enzymatic hydrocarbon hydroxylation, especially by cytochrome P450. Copyright (C) 1999 Elsevier Science Inc.

元の言語英語
ページ(範囲)23-34
ページ数12
ジャーナルJournal of Inorganic Biochemistry
78
発行部数1
DOI
出版物ステータス出版済み - 1 15 2000
外部発表Yes

Fingerprint

methane monooxygenase
Hydroxylation
Methane
Catalytic Domain
Iron
Methanol
Diamond
Hydrocarbons
Cytochrome P-450 Enzyme System
Genetic Recombination
Density functional theory
Gases

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Inorganic Chemistry

これを引用

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title = "Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase",
abstract = "A new concerted mechanism is proposed for the conversion of methane to methanol on intermediate Q of soluble methane monooxygenase (sMMO), the active site of which is considered to involve an Fe2(μ-O)2 diamond core. A hybrid density functional theory (DFT) method is used for our mechanistic study on the important reactivity of the bare FeO+ complex and a diiron model of intermediate Q. The reaction pathway for the methane hydroxylation on the diiron complex is essentially identical to that for the gas-phase reaction by the bare FeO+ complex. Methane is highly activated on the dinuclear iron model through the formation of a methane complex, in which a coordinatively unsaturated iron plays a central role in the bonding interaction between the diiron model and substrate methane. A H atom abstraction via a four-centered transition state and a recombination of the OH and CH3 groups via a three-centered transition state successively occur on the dinuclear iron-oxo species, leading to the formation of a methanol complex that corresponds to intermediate T. These electronic processes take place in a concerted manner. Our mechanism for methane hydroxylation by sMMO is different from the radical mechanism that has been widely accepted for enzymatic hydrocarbon hydroxylation, especially by cytochrome P450. Copyright (C) 1999 Elsevier Science Inc.",
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