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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Vydané v:	Chemistry : a European journal Ročník 20; číslo 48; s. 15686 - 15691
Hlavní autori:	Jastrzebski, Robin, Quesne, Matthew G., Weckhuysen, Bert M., de Visser, Sam P., Bruijnincx, Pieter C. A.
Médium:	Journal Article
Jazyk:	English
Vydavateľské údaje:	Weinheim WILEY-VCH Verlag 24.11.2014 WILEY‐VCH Verlag Wiley Subscription Services, Inc
Predmet:	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
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Popis
Shrnutí:	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.
Bibliografia:	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 content type line 14 content type line 23
ISSN:	0947-6539 1521-3765 1521-3765
DOI:	10.1002/chem.201404988