A Strained Ion Pair Permits Carbon Dioxide Fixation at Atmospheric Pressure by C-H H-Bonding Organocatalysis

The cycloadditions of carbon dioxide into epoxides to afford cyclic carbonates by H-bond donor (HBD) and onium halide (X) cocatalysis have emerged as a key strategy for CO₂ fixation. However, if the HBD is also a halide receptor, the two will quench each other, decreasing the catalytic activity. Here, we propose a strained ion pair tris(alkylamino)cyclopropenium halide (TAC·X), in which TAC repels X. TAC possesses a positively charged cyclopropenium core that makes the vicinal C-H or N-H a nonclassical HBD. The interionic strain within TAC·X makes TAC a more electrophilic HBD, allowing it to activate the oxygen of the epoxide and making X more nucleophilic and better able to attack the methylene carbon of the epoxide. NMR titration spectra and computational studies were employed to probe the mechanism of the cycloaddition of CO₂ to epoxides reactions under the catalysis of TAC·X. The ¹H and ¹³C{¹H}NMR titration spectra of the catalyst with the epoxide substrate unambiguously confirmed H-bonding between TAC and the epoxide. DFT computational studies identified the transition states in the ring-opening of the epoxide (TS1) and in the ring-closure of the cyclic carbonate (TS2).