An atomically precise Au₁₀(DPPF)₄PPh₃ cluster catalyst for N-hydroformylation of amines

Heterogeneous catalysis is crucially important for the well-being of society, and new catalysts are continuously discovered to improve chemical processes. Here we report a catalytic system based on an atomically precise Au₁₀(DPPF)₄PPh₃ (DPPF = bidentate 1,1'-bis(diphenylphosphino)ferrocene) cluster, where two functional units are combined into one catalyst for N-hydroformylation of pyrrolidine with CO₂ and H₂. The two units execute their respective roles, including two types of ligands that mediate the structural framework and further reinforce the catalytic stability of the cluster, and a metal core consisting of ten gold atoms that are all potentially active sites participating in the hydrogenation of CO₂ toward the key intermediate, such as formic acid. Sequentially, formylation proceeds via a relay migration of protons along a proposed transition state originating from the intermediate and pyrrolidine, thereby breaking the N-H bond and constructing the C-N bond. The synergy between the active sites and the neighbouring environment therefore enables optimal activity and stability of the cluster catalyst, outperforming most catalysts reported under comparable conditions.