Heterogeneous Cross-Coupling over Gold Nanoclusters

Au clusters with the precise numbers of gold atoms, a novel nanogold material, have recently attracted increasing interest in the nanoscience because of very unique and unexpected properties. The unique interaction and electron transfer between gold clusters and reactants make the clusters promising catalysts during organic transformations. The Au(n)L(m) nanoclusters (where L represents organic ligands and n and m mean the number of gold atoms and ligands, respectively) have been well investigated and developed for selective oxidation, hydrogenation, photo-catalysis, and so on. These gold clusters possess unique frameworks, providing insights into the catalytic processes and an excellent arena to correlate the atomic frameworks with their intrinsic catalytic properties and to further investigate the tentative reaction mechanisms. This review comprehensively summarizes the very latest advances in the catalytic applications of the Au nanoclusters for the C−C cross-coupling reactions, e.g., Ullmann, Sonogashira, Suzuki cross-couplings, and A(3)−coupling reactions. It is found that the proposed catalytically active sites are associated with the exposure of gold atoms on the surface of the metal core when partial capping organic ligands are selectively detached under the reaction conditions. Finally, the tentative catalytic mechanisms over the ligand-capped Au nanoclusters and the relationship of structure and catalytic performances at the atomic level using computational methods are explored in detail.