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

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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-η12-peroxoCuICuII species.

Original languageEnglish
Pages (from-to)838-845
Number of pages8
JournalInorganic Chemistry
Volume48
Issue number3
DOIs
Publication statusPublished - Feb 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

Cite this

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

In: Inorganic Chemistry, Vol. 48, No. 3, 02.02.2009, p. 838-845.

Research output: Contribution to journalArticle

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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.",
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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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