Dioxygen cleavage and methane activation on diiron enzyme models: A theoretical study

Kazunari Yoshizawa, Takehiro Ohta, Tokio Yamabe, Roald Hoffmann

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90 Citations (Scopus)


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
Issue number50
Publication statusPublished - Dec 17 1997
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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