title: Unexpected bond activations promoted by palladium nanoparticles.
abstract: Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (d(mean) = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs.
authors.affiliation: Depto. de Química Inorgánica, Facultad de Química, Universidad Nacional Autónoma de México, Av. Universidad 3000, 04510 D.F., México. erikam@unam.mx.
authors.forename: A M
authors.initials: AM
authors.lastname: López-Vinasco
authors.forename: I
authors.initials: I
authors.lastname: Favier
authors.forename: C
authors.initials: C
authors.lastname: Pradel
authors.forename: L
authors.initials: L
authors.lastname: Huerta
authors.forename: I
authors.initials: I
authors.lastname: Guerrero-Ríos
authors.forename: E
authors.initials: E
authors.lastname: Teuma
authors.forename: M
authors.initials: M
authors.lastname: Gómez
authors.forename: E
authors.initials: E
authors.lastname: Martin