Catalytic Activity of Water-Soluble Palladium Nanoparticles with Anionic and Cationic Capping Ligands for Reduction, Oxidation, and C-C Coupling Reactions in Water.

Abstract

The availability of water-soluble nanoparticles allows catalytic reactions to occur in highly desirable green environments. The catalytic activity and selectivity of water-soluble palladium nanoparticles capped with 6-(carboxylate)hexanethiolate (C6-PdNP) and 5-(trimethylammonio)pentanethiolate (C5-PdNP) were investigated for the reduction of 4-nitrophenol, the oxidation of α,β-conjugated aldehydes, and the C-C coupling of phenylboronic acid. The study showed that between the two PdNPs, C6-PdNP exhibits better catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride and the selective oxidation of conjugated aldehydes to conjugated carboxylic acids. For the latter reaction, molecular hydrogen (H₂) and H₂O act as oxidants for the surface palladium atoms on PdNPs and conjugated aldehyde substrates, respectively. The results indicated that the competing addition activities of Pd-H and H₂O toward the π-bond of different unsaturated substrates promote either reduction or oxidation reactions under mild conditions in organic solvent-free environments. In comparison, C5-PdNP exhibited higher catalytic activity for the C-C coupling of phenylboronic acid. Gas chromatography-mass spectrometry (GC-MS) was mainly used as an analytical technique to examine the products of catalytic reactions.