title: Evidencing an inner-sphere mechanism for NHC-Au(I)-catalyzed carbene-transfer reactions from ethyl diazoacetate.
abstract: Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA) and styrene or methanol catalyzed by the [IPrAu](+) core (IPr = 1,3-bis(diisopropylphenyl)imidazole-2-ylidene) have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol) takes place in the coordination sphere of Au(I) by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechanisms for Au(I)-catalyzed reactions.
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Campus de El Carmen, 21007 Huelva, Spain.
authors.forename: Manuel R
authors.initials: MR
authors.lastname: Fructos
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Campus de El Carmen, 21007 Huelva, Spain.
authors.forename: Juan
authors.initials: J
authors.lastname: Urbano
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Campus de El Carmen, 21007 Huelva, Spain.
authors.forename: M Mar
authors.initials: MM
authors.lastname: Díaz-Requejo
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Campus de El Carmen, 21007 Huelva, Spain.
authors.forename: Pedro J
authors.initials: PJ
authors.lastname: Pérez
keywords: O–H functionalization; carbene transfer; gold catalysis; inner sphere; olefin cyclopropanation