Facile Synthesis of Palladium Nanoparticles Protected with Alkanethiolates Functionalized with Organometallic Fragments

A synthesis of organometallic functionalized thiol-protected palladium nanoparticles (Pd NPs) is presented. The first step of the procedure consists of forming starting Pd NPs protected with two different ligands. The shorter one, hexanethiolate, is introduced to provide solubility to the system in organic solvents, and the larger is the alkane thiolate HS(CH2)(11)OOCC6H4PPh2 (L), equipped with a terminal free phosphine group. Reaction of the latter nanoparticles, NP1, with appropriate organometallic derivatives, permitted the isolation of soluble Pd NPs displaying at the periphery the metal units PdCl(eta(3)-2-MeC3H4) (NP2), IrCl(cod) (NP3), RuCl2(p-cymene) (NP4), RhCl(cod) (NP5), RhCl(CO) (NP6), and Rh(cod)(+)(NP7). The palladium nanopartides were examined using NMR, FTIR, HRTEM, TGA, and XPS.