Catalytic N‐Formylation of CO₂ by Atomically Precise Au₈Pd₁(DPPF)₄²⁺ Clusters into a Two‐Dimensional Metal–Organic Framework

Abstract By highly efficient ligand‐exchange strategy, atomically precise Au 8 Pd 1 (PPh 3 ) 8 2+ (PPh 3 =triphenylphosphine) cluster can be transformed into a Au 8 Pd 1 (DPPF) 4 2+ (DPPF=1,1′‐bis(diphenylphosphino)ferrocene) cluster that can maintain the atomic‐packing structure but overcome the lability of Au 8 Pd 1 (PPh 3 ) 8 2+ . Catalytic evaluation for the CO 2 hydrogenation coupled with o‐phenylenediamine demonstrates that the Au 8 Pd 1 (DPPF) 4 2+ catalyst can remarkably enhance both activity and stability compared to the Au 8 Pd 1 (PPh 3 ) 8 2+ catalyst. More notably, the direct construction of a two‐dimensional metal–organic framework (2D MOF) can be elaborately accomplished in the formylation process of o‐phenylenediamine, CO 2 and H 2 with zinc nitrate enabled by the Au 8 Pd 1 (DPPF) 4 2+ catalyst. The 2D MOF further enables the capture and transformation of CO 2 to combine in the organic synthesis with epoxides under mild conditions. This work provides opportunities for creating highly active cluster sites for the chemical recycling of CO 2 .