Experimental and Computational Evidence for the Mechanism of Intradiol Catechol Dioxygenation by Non-Heme Iron(III) Complexes

Catechol intradiol dioxygenation is a unique reaction catalyzed by iron‐dependent enzymes and non‐heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational...

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Veröffentlicht in:Chemistry : a European journal Jg. 20; H. 48; S. 15686 - 15691
Hauptverfasser: Jastrzebski, Robin, Quesne, Matthew G., Weckhuysen, Bert M., de Visser, Sam P., Bruijnincx, Pieter C. A.
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim WILEY-VCH Verlag 24.11.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Schlagworte:
biomimetic models
Bonding
Carbon
Catalysis
Catechol
Catechols
Chemical reactions
Chemistry
Cleavage
Communications
Computation
Computers, Molecular
density functional theory
enzyme models
Ferric Compounds - chemistry
Iron
Kinetics
Models, Molecular
Molecular Structure
Oxygen - chemistry
reactivity
biomimetic models
reactivity
kinetics
enzyme models
density functional theory
ISSN:0947-6539, 1521-3765, 1521-3765
Online-Zugang:Volltext
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Zusammenfassung:Catechol intradiol dioxygenation is a unique reaction catalyzed by iron‐dependent enzymes and non‐heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational modelling of multiple iron(III) catecholato complexes, we have elucidated the catechol cleavage mechanism and show that oxygen binds the iron center by partial dissociation of the substrate from the iron complex. The iron(III) superoxide complex that is formed subsequently attacks the carbon atom of the substrate by a rate‐determining CO bond formation step. Reaction mechanism: The combination of experimental and computational work has revealed that in catechol intradiol dioxygenation, oxygen binds to iron first, facilitated by partial dissociation and one‐electron oxidation of the substrate (see scheme). The subsequent attack of oxygen on the substrate carbon atom was shown to be the rate‐determining step in this unique reaction.
Bibliographie:istex:566C321FE77942FD4FC1E44E92195BF2ADD51576
Funded Access
ArticleID:CHEM201404988
Netherlands Organization for Scientific Research (NWO)
BBSRC
ark:/67375/WNG-953V6ZK2-3
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201404988