title: Catalytic Activity of Cationic and Neutral Silver(I)-XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza-Diels-Alder Coupling Reactions.
abstract: Cationic and neutral silver(I)-L complexes (L=Buchwald-type biaryl phosphanes) with nitrogen co-ligands or organosulfonate counter ions have been synthesised and characterised through their structural and spectroscopic properties. At room temperature, both cationic and neutral silver(I)-L complexes are extremely active catalysts in the promotion of the single and double A(3) coupling of terminal (di)alkynes, pyrrolidine and formaldehyde. In addition, the aza-Diels-Alder two- and three-component coupling reactions of Danishefsky's diene with an imine or amine and aldehyde are efficiently catalysed by these cationic or neutral silver(I)-L complexes. The solvent influences the catalytic performance due to limited complex solubility or solvent decomposition and reactivity. The isolation of new silver(I)-L complexes with reagents as ligands lends support to mechanistic proposals for such catalytic processes. The activity, stability and metal-distal arene interaction of these silver(I)-L catalysts have been compared with those of analogous cationic gold(I) and copper(I) complexes.
authors.affiliation: Instituto Universitario de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain). grirrane@itq.upv.es.
authors.forename: Abdessamad
authors.initials: A
authors.lastname: Grirrane
authors.affiliation: Instituto de Investigaciones Químicas IIQ-CSIC-US, Consejo Superior de Investigaciones Científicas - Universidad de Sevilla, Av. Américo, Vespucio 49, 41092 Sevilla (Spain).
authors.forename: Eleuterio
authors.initials: E
authors.lastname: Álvarez
authors.affiliation: Instituto Universitario de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain). hgarcia@qim.upv.es.
authors.forename: Hermenegildo
authors.initials: H
authors.lastname: García
authors.affiliation: Instituto Universitario de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain). acorma@itq.upv.es.
authors.forename: Avelino
authors.initials: A
authors.lastname: Corma
keywords: P ligands; cross-coupling; homogeneous catalysis; reaction mechanisms; silver