Nonradical mechanism for methane hydroxylation by iron-oxo complexes

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Abstract

A nonradical mechanism for methane hydroxylation by the bare FeO + complex, Fe-ZSM-5 zeolite, and soluble methane monooxygenase is proposed from quantum chemical calculations. This mechanism is applicable when a metal-oxo species is coordinatively unsaturated. Direct interaction between methane and a metal active center can form a weakly bound methane complex in the initial stages of this reaction. Subsequent C-H bond cleavage to form an intermediate with an HO-Fe-CH3 moiety in a nonradical manner and recombination of the resultant OH and CH3 ligands take place at a metal active center to form a final methanol complex. Thus, this is a nonradical, two-step reaction. The fact that methyl radical is 10-20 kcal/mol less stable than secondary and tertiary carbon radicals and benzyl radicals leads us to propose this mechanism.

Original languageEnglish
Pages (from-to)375-382
Number of pages8
JournalAccounts of Chemical Research
Volume39
Issue number6
DOIs
Publication statusPublished - Jun 1 2006

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Hydroxylation
Methane
Iron
Metals
methane monooxygenase
Methanol
Carbon
Ligands

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Nonradical mechanism for methane hydroxylation by iron-oxo complexes. / Yoshizawa, Kazunari.

In: Accounts of Chemical Research, Vol. 39, No. 6, 01.06.2006, p. 375-382.

Research output: Contribution to journalArticle

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AB - A nonradical mechanism for methane hydroxylation by the bare FeO + complex, Fe-ZSM-5 zeolite, and soluble methane monooxygenase is proposed from quantum chemical calculations. This mechanism is applicable when a metal-oxo species is coordinatively unsaturated. Direct interaction between methane and a metal active center can form a weakly bound methane complex in the initial stages of this reaction. Subsequent C-H bond cleavage to form an intermediate with an HO-Fe-CH3 moiety in a nonradical manner and recombination of the resultant OH and CH3 ligands take place at a metal active center to form a final methanol complex. Thus, this is a nonradical, two-step reaction. The fact that methyl radical is 10-20 kcal/mol less stable than secondary and tertiary carbon radicals and benzyl radicals leads us to propose this mechanism.

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