Dioxygen cleavage and methane activation on diiron enzyme models

A theoretical study

Kazunari Yoshizawa, Takehiro Ohta, Tokio Yamabe, Roald Hoffmann

Research output: Contribution to journalArticle

81 Citations (Scopus)

Abstract

Two possible mechanisms for dioxygen cleavage on non-heme diiron enzyme models are studied with an approximate molecular orbital method, the extended Huckel method. Diiron peroxo model complexes with different μ-η11-O2 and μ-η22-O2 binding modes are distorted to corresponding dioxo complexes along an assumed O-O bond cleavage reaction coordinate. Fragment molecular orbital (FMO) and Walsh diagram analyses clarify the bonding and orbital interactions. While the π(g)* orbitals of O2 are initially occupied by two electrons, in the first dioxygen binding step two other electrons are effectively transferred from the 't(2g)' block to O2 to form O22-. To cleave the dioxygen O-O bond, it is necessary further to fill the σ(u)* orbital (high lying and unoccupied in the peroxide). The computations suggest that the μ-ν11-O2 mode is more effective for electron transfer from the d-block orbitals to the σ(u)*. Our calculations indicate that a C(3v)- or D(2d)-distorted methane can be activated if a coordinatively unsaturated iron, which has been proposed to exist in the diamond Fe2(μ- O)2 core of intermediate Q of methane monooxygenase, is generated. The complex is suggested to include a five-coordinate carbon species with an Fe- CH4 bond. We propose possible concerted reaction pathways for the conversion of methane to methanol on the supposed diiron active site of methane monooxygenase. Inversion at a five-coordinate carbon species is suggested to reasonably occur in an initially formed complex of methane and a model of intermediate Q, leading to inversion of stereochemistry at a labeled carbon center.

Original languageEnglish
Pages (from-to)12311-12321
Number of pages11
JournalJournal of the American Chemical Society
Volume119
Issue number50
DOIs
Publication statusPublished - Dec 17 1997

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methane monooxygenase
Methane
Theoretical Models
Carbon
Enzymes
Chemical activation
Molecular orbitals
Electrons
Oxygen
Conversion Disorder
Stereochemistry
Diamond
Peroxides
Methanol
Catalytic Domain
Iron
Diamonds

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Dioxygen cleavage and methane activation on diiron enzyme models : A theoretical study. / Yoshizawa, Kazunari; Ohta, Takehiro; Yamabe, Tokio; Hoffmann, Roald.

In: Journal of the American Chemical Society, Vol. 119, No. 50, 17.12.1997, p. 12311-12321.

Research output: Contribution to journalArticle

Yoshizawa, Kazunari ; Ohta, Takehiro ; Yamabe, Tokio ; Hoffmann, Roald. / Dioxygen cleavage and methane activation on diiron enzyme models : A theoretical study. In: Journal of the American Chemical Society. 1997 ; Vol. 119, No. 50. pp. 12311-12321.
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