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

By highly efficient ligand‐exchange strategy, atomically precise Au8Pd1(PPh3)82+ (PPh3=triphenylphosphine) cluster can be transformed into a Au8Pd1(DPPF)42+ (DPPF=1,1′‐bis(diphenylphosphino)ferrocene) cluster that can maintain the atomic‐packing structure but overcome the lability of Au8Pd1(PPh3)82+. Catalytic evaluation for the CO2 hydrogenation coupled with o‐phenylenediamine demonstrates that the Au8Pd1(DPPF)42+ catalyst can remarkably enhance both activity and stability compared to the Au8Pd1(PPh3)82+ 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, CO2 and H2 with zinc nitrate enabled by the Au8Pd1(DPPF)42+ catalyst. The 2D MOF further enables the capture and transformation of CO2 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 CO2. In this work, we report an atomically precise Au8Pd1(DPPF)42+ cluster with a highly robust structure that can catalyze the CO2 hydrogenation coupled with o‐phenylenediamine to synthesize benzimidazole and can further react with Zn(NO3)2 for the feasible synthesis of a new two‐dimensional metal–organic framework.