Catalytic N-Formylation of CO by Atomically Precise AuPd(DPPF) Clusters into a Two-Dimensional Metal-Organic Framework.

By highly efficient ligand-exchange strategy, atomically precise AuPd(PPh) (PPh=triphenylphosphine) cluster can be transformed into a AuPd(DPPF) (DPPF=1,1'-bis(diphenylphosphino)ferrocene) cluster that can maintain the atomic-packing structure but overcome the lability of AuPd(PPh) . Catalytic evaluation for the CO hydrogenation coupled with o-phenylenediamine demonstrates that the AuPd(DPPF) catalyst can remarkably enhance both activity and stability compared to the AuPd(PPh) 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 and H with zinc nitrate enabled by the AuPd(DPPF) catalyst. The 2D MOF further enables the capture and transformation of CO 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.