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

Research output: Contribution to journalArticle

77 Citations (Scopus)

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

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Comparison of the reactivity of bis(μ-oxo)Cu<sup>II</sup>Cu <sup>III</sup> and Cu<sup>III</sup>Cu<sup>III</sup> species to methane'. Together they form a unique fingerprint.

  • Cite this