Comparison of the reactivity of bis(μ-oxo)CuIICu III and CuIIICuIII species to methane

研究成果: ジャーナルへの寄稿記事

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Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory (DFT) calculations. The electronic and structural properties of the dinuclear copper species of bis(μ-oxo)CuIICuIII and Cu IIICuIII are discussed with respect to the C-H bond activation of methane. The bis(μ-oxo)CuIICuIII species is highly reactive and considered to be an active species for the conversion of methane to methanol by pMMO, whereas the bis(μ-oxu)CuIIICu III species is unable to react with methane as it is. If a Cu-O bond of the bis(μ-oxo)CuIIICuIII species is cleaved, the resultant CuIIICuIII species, in which only one oxo ligand bridges the two copper ions, can activate methane. However, its energetics for methane hydroxylation is less favorable than that by the bis(μ-oxo)Cu IICuIII species. The DFT calculations show that the bis(μ-oxo)CuIICuIII species is more effective for the activation of methane than the bis(μ-oxu)CuIIICuII species. The reactive bis(μ-oxo)CuIICuIII species can be created either from the electron injection to the bis(μ-oxo)Cu IIICuIII species or from the O-O bond cleavage in the μ-η12-peroxoCuICuII species.

元の言語英語
ページ(範囲)838-845
ページ数8
ジャーナルInorganic Chemistry
48
発行部数3
DOI
出版物ステータス出版済み - 2 2 2009

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Methane
methane
reactivity
methane monooxygenase
Copper
Hydroxylation
Density functional theory
Chemical activation
copper
particulates
Electron injection
activation
density functional theory
Electronic properties
Methanol
Structural properties
Ions
Ligands
cleavage
methyl alcohol

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

これを引用

Comparison of the reactivity of bis(μ-oxo)CuIICu III and CuIIICuIII species to methane. / Shiota, Yoshihito; Yoshizawa, Kazunari.

:: Inorganic Chemistry, 巻 48, 番号 3, 02.02.2009, p. 838-845.

研究成果: ジャーナルへの寄稿記事

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title = "Comparison of the reactivity of bis(μ-oxo)CuIICu III and CuIIICuIII species to methane",
abstract = "Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory (DFT) calculations. The electronic and structural properties of the dinuclear copper species of bis(μ-oxo)CuIICuIII and Cu IIICuIII are discussed with respect to the C-H bond activation of methane. The bis(μ-oxo)CuIICuIII species is highly reactive and considered to be an active species for the conversion of methane to methanol by pMMO, whereas the bis(μ-oxu)CuIIICu III species is unable to react with methane as it is. If a Cu-O bond of the bis(μ-oxo)CuIIICuIII species is cleaved, the resultant CuIIICuIII species, in which only one oxo ligand bridges the two copper ions, can activate methane. However, its energetics for methane hydroxylation is less favorable than that by the bis(μ-oxo)Cu IICuIII species. The DFT calculations show that the bis(μ-oxo)CuIICuIII species is more effective for the activation of methane than the bis(μ-oxu)CuIIICuII species. The reactive bis(μ-oxo)CuIICuIII species can be created either from the electron injection to the bis(μ-oxo)Cu IIICuIII species or from the O-O bond cleavage in the μ-η1-η2-peroxoCuICuII species.",
author = "Yoshihito Shiota and Kazunari Yoshizawa",
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journal = "Inorganic Chemistry",
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T1 - Comparison of the reactivity of bis(μ-oxo)CuIICu III and CuIIICuIII species to methane

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

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N2 - Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory (DFT) calculations. The electronic and structural properties of the dinuclear copper species of bis(μ-oxo)CuIICuIII and Cu IIICuIII are discussed with respect to the C-H bond activation of methane. The bis(μ-oxo)CuIICuIII species is highly reactive and considered to be an active species for the conversion of methane to methanol by pMMO, whereas the bis(μ-oxu)CuIIICu III species is unable to react with methane as it is. If a Cu-O bond of the bis(μ-oxo)CuIIICuIII species is cleaved, the resultant CuIIICuIII species, in which only one oxo ligand bridges the two copper ions, can activate methane. However, its energetics for methane hydroxylation is less favorable than that by the bis(μ-oxo)Cu IICuIII species. The DFT calculations show that the bis(μ-oxo)CuIICuIII species is more effective for the activation of methane than the bis(μ-oxu)CuIIICuII species. The reactive bis(μ-oxo)CuIICuIII species can be created either from the electron injection to the bis(μ-oxo)Cu IIICuIII species or from the O-O bond cleavage in the μ-η1-η2-peroxoCuICuII species.

AB - Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory (DFT) calculations. The electronic and structural properties of the dinuclear copper species of bis(μ-oxo)CuIICuIII and Cu IIICuIII are discussed with respect to the C-H bond activation of methane. The bis(μ-oxo)CuIICuIII species is highly reactive and considered to be an active species for the conversion of methane to methanol by pMMO, whereas the bis(μ-oxu)CuIIICu III species is unable to react with methane as it is. If a Cu-O bond of the bis(μ-oxo)CuIIICuIII species is cleaved, the resultant CuIIICuIII species, in which only one oxo ligand bridges the two copper ions, can activate methane. However, its energetics for methane hydroxylation is less favorable than that by the bis(μ-oxo)Cu IICuIII species. The DFT calculations show that the bis(μ-oxo)CuIICuIII species is more effective for the activation of methane than the bis(μ-oxu)CuIIICuII species. The reactive bis(μ-oxo)CuIICuIII species can be created either from the electron injection to the bis(μ-oxo)Cu IIICuIII species or from the O-O bond cleavage in the μ-η1-η2-peroxoCuICuII species.

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