title: A kinetico-mechanistic study on the C-H bond activation of primary benzylamines; cooperative and solid-state cyclopalladation on dimeric complexes.
abstract: The cyclometallation reactions of dinuclear μ-acetato complexes of the type [Pd(AcO)(μ-AcO)L]2 (L = 4-RC6H4CH2NH2, R = H, Cl, F, CF3), a process found to occur readily even in the solid state, have been studied from a kinetico-mechanistic perspective. Data indicate that the dinuclear acetato bridged derivatives are excellent starting materials to activate carbon-hydrogen bonds in a facile way. In all cases the established concerted ambiphilic proton abstraction by a coordinated acetato ligand has been proved. The metallation has also been found to occur in a cooperative manner, with the metallation of the first palladium unit of the dimeric complex being rate determining; no intermediate mono-metallated compounds are observed in any of the processes. The kinetically favoured bis-cyclopalladated compound obtained after complete C-H bond activation does not correspond to the final isolated XRD-characterized complexes. This species, bearing the classical open-book dimeric form, has a much more complex structure than the final isolated compound, with different types of acetato ligands.
authors.affiliation: Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain. jaume.granell@qi.ub.es manel.martinez@qi.ub.es.
authors.forename: Helena
authors.initials: H
authors.lastname: Font
authors.forename: Mercè
authors.initials: M
authors.lastname: Font-Bardia
authors.forename: Kerman
authors.initials: K
authors.lastname: Gómez
authors.forename: Gabriel
authors.initials: G
authors.lastname: González
authors.forename: Jaume
authors.initials: J
authors.lastname: Granell
authors.forename: Israel
authors.initials: I
authors.lastname: Macho
authors.forename: Manuel
authors.initials: M
authors.lastname: Martínez