Atomically precise copper clusters with dual sites for highly chemoselective and efficient hydroboration

Abstract The hydroboration of alkynes into vinylboronate esters is a vital transformation, but achieving high chemoselectivity of targeted functional groups and an appreciable turnover number is a considerable challenge. Herein, we develop two dynamically regulating dual-catalytic-site copper clusters (Cu 4 NC and Cu 8 NC) bearing N-heterocyclic thione ligands that endow Cu 4 NC and Cu 8 NC catalysts with performance. In particular, the performance of microcrystalline Cu 4 NC in hydroboration is characterized by a high turnover number (77786), a high chemoselectivity, high recovery and reusability under mild conditions. Mechanistic studies and density functional theory calculations reveal that, compared with the Cu 8 NC catalyst, the Cu 4 NC catalyst has a lower activation energy for hydroboration, accounting for its high catalytic activity. This work reveals that precisely constructed cluster catalysts with dual catalytic sites may provide a way to substantially improve catalytic properties by fully leveraging synergistic interactions and dynamic ligand effects, thus promoting the development of cluster catalysts.