A Versatile Approach to the Synthesis of Functionalized Thiol-Protected Palladium Nanoparticles

A synthesis of variably functionalized thiol-protected palladium nanoparticles (Pd-NPs) is presented. The nanoparticle syntheses are performed in acetone/water or tetrahydrofuranwater solutions, without making use of either phase-transfer agents or complex purification procedures of the as-synthesized nanoparticles. Small and mostly monodisperse thiol-protected Pd nanoparticles (Pd-NPs ~ 2 nm) have been prepared with 11-mercaptoundecanoic acid (MUA), 9-mercapto-1-nonanol (MN), 1-dodecanethiol (DT), or mixtures thereof, and a simple scale-up synthesis is also proposed. The role of PdII-thiolate species as metal precursors in the stage of nanoparticle synthesis and the influence of the reaction parameters on the final Pd-NPs size and size distribution are discussed. The formation of mixed-monolayer protected nanoparticles is achieved, with the final monolayer composition dictated by the thiols, initial molar ratio. Overall, the procedure presented here allows the preparation of functionalized nanoparticles with a high density of functional groups at the edge of the monolayer, with no need of place-exchange reactions. Specific postfunctionalization procedures conducted at the acid groups of the MUA-Pd monolayer are reported so as to widen the potential applicability of these amphiphilic nanoparticle precursors with respect to different applications in the field of material science. Finally, the successful use and the easy recycling/reuse of the Pd-NPs in a model Suzuki cross-coupling reaction are presented.