Palladium nanoparticles peripherally functionalized with "RuCl2(p-cymene)" (NP2), "RhCl(cod)" (NP3) and "PdCl(eta(3)-2-MeC3H4)" (NP4) units show catalytic activity in C-C coupling reactions, hydrogenation and hydrovinylation processes. We report for the first time an example of a catalytic precursor for the hydrovinylation/C-C coupling sequential process by using the two catalytic centres displayed by NP4, the Pd core and the PdCl(eta(3)-2-MeC3H4) moieties. (C) 2013 Elsevier B.V. All rights reserved.