Is the Suzuki-Miyaura Cross-Coupling Reaction in the Presence of Pd Nanoparticles Heterogeneously or Homogeneously Catalyzed? An Interfacial Surface-Enhanced Raman Spectroscopy Study.

Abstract

Pd-catalyzed Suzuki-Miyaura C-C cross-coupling is very central in chemistry. The question of whether the catalysis by using Pd nanoparticles (NPs) is heterogeneous (on the Pd surface) or homogeneous (by soluble Pd released from the NP surface) remains under fundamental physicochemical debate. This work reports on the in situ characterization of the Suzuki-Miyaura cross-coupling reactions by using surface-enhanced Raman spectroscopy. We find clear evidence of heterogeneous catalysis on the Pd surface. In contrast, the soluble Pd species leaching into the solution cannot catalyze the reaction, indicating a direct contact of the aryl halides with the metal surface is a prerequisite. Accordingly, the surface ligands and charge of the Pd NPs, which determine the molecule-metal contact, are very important in the couplings. By a simple exchange of the surface ligand or a surface modification of the support material, the catalytic activity of Pd NPs is improved due to the enhanced electric attraction between the metal and the reactant molecules.