Document Detail


A diiron(IV) complex that cleaves strong C-H and O-H bonds.
MedLine Citation:
PMID:  19885382     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The controlled cleavage of strong C-H bonds like those of methane poses a significant challenge for chemists. In nature methane is oxidized to methanol by soluble methane monooxygenase via a diiron(IV) intermediate called Q. To model the chemistry of MMO-Q, an oxo-bridged diiron(IV) complex has been generated by electrochemical oxidation and characterized by several spectroscopic methods. This novel species has an Fe(IV/III) redox potential of +1.50 V vs. ferrocene (>2 V vs. NHE), the highest value thus far determined electrochemically for an iron complex. This species is quite an effective oxidant. It can attack C-H bonds as strong as 100 kcal mol(-1) and reacts with cyclohexane a hundred- to a thousand-fold faster than mononuclear Fe(IV)=O complexes of closely related ligands. Strikingly, this species can also cleave the strong O-H bonds of methanol and tert-butanol instead of their weaker C-H bonds, representing the first example of O-H bond activation for iron complexes.
Authors:
Dong Wang; Erik R Farquhar; Audria Stubna; Eckard Münck; Lawrence Que
Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.    
Journal Detail:
Title:  Nature chemistry     Volume:  1     ISSN:  1755-4349     ISO Abbreviation:  Nat Chem     Publication Date:  2009 May 
Date Detail:
Created Date:  2011-03-07     Completed Date:  2011-05-16     Revised Date:  2014-09-16    
Medline Journal Info:
Nlm Unique ID:  101499734     Medline TA:  Nat Chem     Country:  England    
Other Details:
Languages:  eng     Pagination:  145-50     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Biocatalysis
Carbon / chemistry*
Coordination Complexes / chemistry*
Crystallography, X-Ray
Cyclohexanes / chemistry,  metabolism
Hydrogen / chemistry*
Iron / chemistry*
Methanol / chemistry,  metabolism
Molecular Conformation
Oxidation-Reduction
Oxygen / chemistry*
Oxygenases / chemistry,  metabolism
X-Ray Absorption Spectroscopy
Grant Support
ID/Acronym/Agency:
EB-001475/EB/NIBIB NIH HHS; GM-08700/GM/NIGMS NIH HHS; GM-38767/GM/NIGMS NIH HHS; R01 GM038767/GM/NIGMS NIH HHS; R01 GM038767-21/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Coordination Complexes; 0/Cyclohexanes; 48K5MKG32S/Cyclohexane; 7440-44-0/Carbon; 7YNJ3PO35Z/Hydrogen; E1UOL152H7/Iron; EC 1.13.-/Oxygenases; EC 1.14.13.25/methane monooxygenase; S88TT14065/Oxygen; Y4S76JWI15/Methanol
Comments/Corrections
Comment In:
Nat Chem. 2009 May;1(2):109-10   [PMID:  21378820 ]

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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