title: Aryl palladium carbene complexes and carbene-aryl coupling reactions.
abstract: Transmetalation of an aminocarbene moiety from [W(CO)5{C(NEt2)R}] to palladium leads to isolable monoaminocarbene palladium aryl complexes [{Pd(mu-Br)Pf[C(NEt2)R]}2] (R = Me, Ph; Pf = C6F5). When [W(CO)5{C(OMe)R}] is used, the corresponding palladium carbenes cannot be isolated since these putative, more electrophilic carbenes undergo a fast migratory insertion process to give alkyl palladium complexes. These complexes could be stabilized in the eta3-allylic form for R = 2-phenylethenyl or in the less stable eta3-benzylic fashion for R = Ph. Hydrolysis products and a pentafluorophenylvinylic methyl ether (when R = Me) were also observed. The monoaminocarbenes slowly decompose through carbene-aryl coupling to produce the corresponding iminium salts and, depending on the reaction conditions, the corresponding hydrolysis products. The electrophilicity of the carbene carbon, which is mainly determined by the nature of the heteroatom group, controls the ease of evolution by carbene-aryl coupling. Accordingly, no carbene-aryl coupling was observed for a diaminocarbene palladium aryl complex.
authors.affiliation: Química Inorgánica, Facultad de Ciencias Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid, Spain. albeniz@qi.uva.es
authors.forename: Ana C
authors.initials: AC
authors.lastname: Albéniz
authors.forename: Pablo
authors.initials: P
authors.lastname: Espinet
authors.forename: Raúl
authors.initials: R
authors.lastname: Manrique
authors.forename: Alberto
authors.initials: A
authors.lastname: Pérez-Mateo