Fluoro-functionalized polymeric N-heterocyclic carbene-zinc complexes: Efficient catalyst for formylation and methylation of amines with CO₂ as a C1-building block

A fluoro-functionalized polymeric N-heterocyclic carbene (NHC)-Zn complex (F-PNHC-Zn) was designed and synthesized by taking fluorous imidazolium salts as precursors through a two-step alkylation. The resultant F-PNHC-Zn was applied in catalyzing the formylation and methylation of amines using CO₂ as a C1 building block in the presence of organosilane, which showed much higher activity than the corresponding non-fluorous PNHC-Zn under identical conditions. N-Methylanilines with both electron-withdrawing and electron-donating groups all could be converted to the corresponding formamides and methylamines in >90% conversion. Quantitative conversion of N-methylaniline was obtained even under very low CO₂ pressure (0.05 MPa diluted by N₂). Moreover, F-PNHC-Zn was highly stable and easily recyclable for these reactions.