RT journal article
T1 Exceedingly Fast Oxygen Atom Transfer to Olefins via a Catalytically Competent Nonheme Iron Species
A1 Serrano-Plana, Joan
A1 Aguinaco Martín, Almudena
A1 Belda, Raquel
A1 García-España, Enrique
A1 García Basallote, Manuel
A1 Company, Anna
A1 Costas, Miquel
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
K1 epoxidation
K1 kinetics
K1 nonheme iron complexes
K1 olefins
K1 oxidation
AB The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at ¢40 8C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(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.
PB Willey
YR 2016
FD 2016
LK http://hdl.handle.net/10498/20489
UL http://hdl.handle.net/10498/20489
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 21-sep-2026