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DFT study of the mechanism for methane hydroxylation by soluble methane monooxygenase (sMMO): effects of oxidation state, spin state, and coordination number
DFT study of the mechanism for methane hydroxylation by soluble methane monooxygenase (sMMO): effects of oxidation state, spin state, and coordination number
- Source :
- Dalton Trans.. 42:1011-1023
- Publication Year :
- 2013
- Publisher :
- Royal Society of Chemistry (RSC), 2013.
-
Abstract
- The exact structure of the active site of intermediate Q, the methane-oxidizing species of soluble methane monooxygenase (sMMO), and the reaction mechanism of Q with methane molecule are still not fully clear. To gain further insights into the structure and reaction mechanism, five diiron models of Q that differ in shape, oxidation state, spin state, and coordination number of the two iron centers are studied. Different mechanisms in different spin states were explored. Density functional theory (DFT) calculations show that Fe(III)Fe(IV)(μ-O)(μ-OH) is more reactive than Fe(IV)(2)(μ-O)(2) in the oxygen-rich environment and that the reactivity of the active core of sMMO-Q is not enhanced by converting its oxo bridge into a terminal ligand. A four-coordinated diiron model is the most effective for methane hydroxylation. Both radical and non-radical intermediates are involved in the reactions for the four-coordinated diiron model.
- Subjects :
- Reaction mechanism
Spin states
biology
Methane monooxygenase
Ligand
Iron
Coordination number
Active site
Electrons
Hydroxylation
Photochemistry
Inorganic Chemistry
chemistry.chemical_compound
Models, Chemical
chemistry
Oxidation state
Catalytic Domain
Oxygenases
biology.protein
Quantum Theory
Thermodynamics
Methane
Oxidation-Reduction
Subjects
Details
- ISSN :
- 14779234 and 14779226
- Volume :
- 42
- Database :
- OpenAIRE
- Journal :
- Dalton Trans.
- Accession number :
- edsair.doi.dedup.....ccf7a712dbddd40ef35a805d4d2d7a5d
- Full Text :
- https://doi.org/10.1039/c2dt31304a