title: Experimental and computational evidence for the mechanism of intradiol catechol dioxygenation by non-heme iron(III) complexes.
abstract: 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.
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands); The Manchester Institute for Biotechnology and the School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN (UK).
authors.forename: Robin
authors.initials: R
authors.lastname: Jastrzebski
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Quesne
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.forename: Pieter C A
authors.initials: PC
authors.lastname: Bruijnincx
mesh_terms: D002384:Catalysis; D002396:Catechols; D039301:Computers, Molecular; D005290:Ferric Compounds / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*
chemical_list: D002396:Catechols; D005290:Ferric Compounds; C034221:catechol; D010100:Oxygen
keywords: biomimetic models; density functional theory; enzyme models; kinetics; reactivity