Aminobismuthination of CO2

We report the facile (25 ^oC, 1 atm, <5 minutes) insertion of CO₂ into Bi-N bonds to yield rare examples of bismuth carbamates, whose structures show a μ₂-bridging mode that is hitherto unobserved in s, p, or f-block amide chemistry. The role of ligand and substituent on promoting the controlled aminobismuthination of CO₂ and rendering the bismuth carbamate products stable against thermal decomposition and ligand degradation is revealed.