Predicting the Mechanism and Products of CO2 Capture by Amines in the Presence of H2O

An extensive correlated molecular orbital theory study of the reactions of CO₂ with a range of substituted amines and H₂O in the gas phase and aqueous solution was performed at the G3(MP2) level with a self-consistent reaction field approach. The G3(MP2) calculations were benchmarked at the CCSD(T)/CBS level for NH₃ reactions. A catalytic NH₃ reduces the energy barrier more than a catalytic H₂O for the formation of H₂NCOOH and H₂CO₃. In aqueous solution, the barriers to form both H₂NCOOH and H₂CO₃ are reduced, with HCO₃^- formation possible with one amine present and H₂NCOO^- formation possible only with two amines. Further reactions of H₂NCOOH to form HNCO and urea via the Bazarov reaction have high barriers and are unlikely in both the gas phase and aqueous solution. Reaction coordinates for CH₃NH₂, CH₃CH₂NH₂, (CH₃)₂NH, CH₃CH₂CH₂NH₂, (CH₃)₃N, and DMAP were also calculated. The barrier for proton transfer correlates with amine basicity for alkylammonium carbamate (ΔG^‡_aq < 15 kcal/mol) and alkylammonium bicarbonate (ΔG^‡_aq < 30 kcal/mol) formation. In aqueous solution, carbamic acids, carbamates, and bicarbonates can all form in small amounts with ammonium carbamates dominating for primary and secondary alkylamines. These results have implications for CO₂ capture by amines in both the gas phase and aqueous solution as well as in the solid state, if enough water is present.