title: Copper-Carbene Intermediates in the Copper-Catalyzed Functionalization of O-H Bonds.
abstract: Copper-carbene [Tp(x)Cu=C(Ph)(CO2Et)] and copper-diazo adducts [Tp(x)Cu{η(1)-N2C(Ph)(CO2Et)}] have been detected and characterized in the context of the catalytic functionalization of O-H bonds through carbene insertion by using N2=C(Ph)(CO2Et) as the carbene source. These are the first examples of these type of complexes in which the copper center bears a tridentate ligand and displays a tetrahedral geometry. The relevance of these complexes in the catalytic cycle has been assessed by NMR spectroscopy, and kinetic studies have demonstrated that the N-bound diazo adduct is a dormant species and is not en route to the formation of the copper-carbene intermediate.
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO- Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de Materiales, Universidad de Huelva, 21007 Huelva (Spain), Fax: (+34) 959219942.
authors.forename: Ana
authors.initials: A
authors.lastname: Pereira
authors.affiliation: CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France).|Université de Toulouse; UPS, INPT, LCC, 31077 Toulouse Cedex 4 (France).
authors.forename: Yohan
authors.initials: Y
authors.lastname: Champouret
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO- Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de Materiales, Universidad de Huelva, 21007 Huelva (Spain), Fax: (+34) 959219942.
authors.forename: Carmen
authors.initials: C
authors.lastname: Martín
authors.affiliation: Instituto de Investigaciones Químicas Isla de la Cartuja, CSIC-Universidad de Sevilla, Avenida de Américo Vespucio 49, 41092-Sevilla (Spain).
authors.forename: Eleuterio
authors.initials: E
authors.lastname: Álvarez
authors.affiliation: CNRS; LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France). michel.etienne@lcc-toulouse.fr.|Université de Toulouse; UPS, INPT, LCC, 31077 Toulouse Cedex 4 (France). michel.etienne@lcc-toulouse.fr.
authors.forename: Michel
authors.initials: M
authors.lastname: Etienne
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO- Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de Materiales, Universidad de Huelva, 21007 Huelva (Spain), Fax: (+34) 959219942. trodri@dqcm.uhu.es.
authors.forename: Tomás R
authors.initials: TR
authors.lastname: Belderraín
authors.affiliation: Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO- Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de Materiales, Universidad de Huelva, 21007 Huelva (Spain), Fax: (+34) 959219942. perez@dqcm.uhu.es.
authors.forename: Pedro J
authors.initials: PJ
authors.lastname: Pérez
keywords: NMR spectroscopy; carbenes; copper; diazo compounds; ligands