Two-step concerted mechanism for alkane hydroxylation on the ferryl active site of methane monooxygenase

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Abstract

A two-step concerted mechanism for the conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO) is discussed. We propose that the enzymatic reaction mechanism is essentially the same as that of the gas-phase methane-methanol conversion by the bare FeO+ complex. In the initial stage of our mechanism, the ferryl (Fe-O) 'iron' active site of intermediate Q and substrate methane come into contact to form the initial Q(CH4) complex with an OFe-CH4 bond. The C-H bonds of methane are significantly weakened by the formation of a five-coordinate carbon species, through orbital interactions between a C(3v)- or D(2d)-distorted methane and the Fe-O active site. The important transition state for an H atom abstraction exhibits a four-centered structure. The generated intermediate involves an HO-Fe-CH3 moiety, and it is then converted into the final product complex including methanol as a ligand through a methyl migration that occurs via a three-centered transition state. The two-step concerted mechanism is consistent with recent experiments on regioselectivity of enzyme-catalyzed alkane hydroxylations.

Original languageEnglish
Pages (from-to)318-324
Number of pages7
JournalJournal of Biological Inorganic Chemistry
Volume3
Issue number3
DOIs
Publication statusPublished - Jun 1 1998
Externally publishedYes

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methane monooxygenase
Hydroxylation
Alkanes
Methane
Catalytic Domain
Methanol
Regioselectivity
Carbon
Iron
Gases
Ligands
Atoms

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Inorganic Chemistry

Cite this

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title = "Two-step concerted mechanism for alkane hydroxylation on the ferryl active site of methane monooxygenase",
abstract = "A two-step concerted mechanism for the conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO) is discussed. We propose that the enzymatic reaction mechanism is essentially the same as that of the gas-phase methane-methanol conversion by the bare FeO+ complex. In the initial stage of our mechanism, the ferryl (Fe-O) 'iron' active site of intermediate Q and substrate methane come into contact to form the initial Q(CH4) complex with an OFe-CH4 bond. The C-H bonds of methane are significantly weakened by the formation of a five-coordinate carbon species, through orbital interactions between a C(3v)- or D(2d)-distorted methane and the Fe-O active site. The important transition state for an H atom abstraction exhibits a four-centered structure. The generated intermediate involves an HO-Fe-CH3 moiety, and it is then converted into the final product complex including methanol as a ligand through a methyl migration that occurs via a three-centered transition state. The two-step concerted mechanism is consistent with recent experiments on regioselectivity of enzyme-catalyzed alkane hydroxylations.",
author = "Kazunari Yoshizawa",
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TY - JOUR

T1 - Two-step concerted mechanism for alkane hydroxylation on the ferryl active site of methane monooxygenase

AU - Yoshizawa, Kazunari

PY - 1998/6/1

Y1 - 1998/6/1

N2 - A two-step concerted mechanism for the conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO) is discussed. We propose that the enzymatic reaction mechanism is essentially the same as that of the gas-phase methane-methanol conversion by the bare FeO+ complex. In the initial stage of our mechanism, the ferryl (Fe-O) 'iron' active site of intermediate Q and substrate methane come into contact to form the initial Q(CH4) complex with an OFe-CH4 bond. The C-H bonds of methane are significantly weakened by the formation of a five-coordinate carbon species, through orbital interactions between a C(3v)- or D(2d)-distorted methane and the Fe-O active site. The important transition state for an H atom abstraction exhibits a four-centered structure. The generated intermediate involves an HO-Fe-CH3 moiety, and it is then converted into the final product complex including methanol as a ligand through a methyl migration that occurs via a three-centered transition state. The two-step concerted mechanism is consistent with recent experiments on regioselectivity of enzyme-catalyzed alkane hydroxylations.

AB - A two-step concerted mechanism for the conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO) is discussed. We propose that the enzymatic reaction mechanism is essentially the same as that of the gas-phase methane-methanol conversion by the bare FeO+ complex. In the initial stage of our mechanism, the ferryl (Fe-O) 'iron' active site of intermediate Q and substrate methane come into contact to form the initial Q(CH4) complex with an OFe-CH4 bond. The C-H bonds of methane are significantly weakened by the formation of a five-coordinate carbon species, through orbital interactions between a C(3v)- or D(2d)-distorted methane and the Fe-O active site. The important transition state for an H atom abstraction exhibits a four-centered structure. The generated intermediate involves an HO-Fe-CH3 moiety, and it is then converted into the final product complex including methanol as a ligand through a methyl migration that occurs via a three-centered transition state. The two-step concerted mechanism is consistent with recent experiments on regioselectivity of enzyme-catalyzed alkane hydroxylations.

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