In situ activation of COOH-functionalized ZIF-90-enabled reductive CO2N-formylation.

A heterogeneous ZIF-90-based catalyst functionalized with COOH and with a porous structure was facilely prepared for efficient CO2 adsorption and activation to undergo reductive N-formylation with a wide range of amines (15 examples) to furnish N-formamides (78-94% yields). The -COO- species generated by an in situ interaction with amine acts as a key species for activating hydrosilane to capture CO2, and remarkably facilitates a cascade C-N coupling and hydrogenation process. Our findings show a facile strategy for the rational construction of robust active sites for reductive CO2 valorization.