title: Exceedingly Fast Oxygen Atom Transfer to Olefins via a Catalytically Competent Nonheme Iron Species.
abstract: The reaction of [Fe(CF3 SO3 )2 (PyNMe3 )] with excess peracetic acid at -40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [Fe(III) (OOAc)(PyNMe3 )](2+) and [Fe(V) (O)(OAc)(PyNMe3 )](2+) , in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies. The observed fast reaction rates and high selectivities demonstrate that this metastable compound is a truly competent OAT intermediate of relevance for nonheme iron catalyzed epoxidations.
authors.affiliation: Grup de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Joan
authors.initials: J
authors.lastname: Serrano-Plana
authors.affiliation: Universidad de Cádiz, Facultad de Ciencias, Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Apdo. 40, 11510 Puerto Real, Cádiz, Spain.
authors.forename: Almudena
authors.initials: A
authors.lastname: Aguinaco
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, Paterna, Valencia 2, 46980, Spain.
authors.forename: Raquel
authors.initials: R
authors.lastname: Belda
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, Paterna, Valencia 2, 46980, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: García-España
authors.affiliation: Universidad de Cádiz, Facultad de Ciencias, Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Apdo. 40, 11510 Puerto Real, Cádiz, Spain. manuel.basallote@uca.es.
authors.forename: Manuel G
authors.initials: MG
authors.lastname: Basallote
authors.affiliation: Grup de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. anna.company@udg.edu.
authors.forename: Anna
authors.identifier: 0000-0003-4845-4418
authors.initials: A
authors.lastname: Company
authors.affiliation: Grup de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. miquel.costas@udg.edu.
authors.forename: Miquel
authors.initials: M
authors.lastname: Costas
keywords: epoxidation; kinetics; nonheme iron complexes; olefins; oxidation