Divergent catalytic behaviors of assembled organogold(i) clusters derived from enyne cyclization.

Homogeneous gold catalysis has attracted much recent attention due to diverse activation modes of gold(i) towards unsaturated organic groups. Because of attractive aurophilic interaction, structural transformations of metalated species into high nuclear clusters are often proposed in gold catalysis, while to date little is known about their assembly behaviors and catalytic activity. In this work, based on stoichiometric Au(i)-mediated enyne cyclization reactions, we achieve a discrete vicinal dicarbanion-centered Au intermediate and three assembled Au, Au, and Au clusters held together by several aryl dicarbanions.

Pyridine dicarbanion-bonded Ag organometallic nanoclusters: synthesis and on-surface oxidative coupling reaction.

Highly reactive organometallic nanoclusters generated in metal-catalyzed reactions are pivotal in the comprehension of catalytic mechanisms. Herein, we develop a two-step synthetic method to achieve three unprecedented aryl dicarbanion-bonded Ag nanoclusters by using protective macrocyclic ligands. Firstly, various aryl dicarbanion-Ag cluster intermediates are acquired a silver-mediated annulation reaction within a macrocyclic ligand.