Nonradical mechanism for methane hydroxylation by iron-oxo complexes

Research output: Contribution to journalArticle

91 Citations (Scopus)

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

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Nonradical mechanism for methane hydroxylation by iron-oxo complexes'. Together they form a unique fingerprint.

  • Cite this