Aromaticity-promoted CO₂ Capture by P/N-Based Frustrated Lewis Pairs: A Theoretical Study

Carbon dioxide (CO₂ , a common combustion pollutant) releasing continuously into the atmosphere is primarily responsible for the rising atmospheric temperature. Therefore, CO₂ sequestration has been an indispensable area of research for the past several decades. On the other hand, the concept of aromaticity is often employed in designing chemical reactions and metal-free frustrated Lewis pairs (FLPs) have proved ideal reagents to achieve CO₂ reduction. However, considering FLP and aromaticity together is less developed in CO₂ capture. Here we report theoretical investigations on the aromaticity-promoted CO₂ activation, involving heterocyclopentadiene-bridged P/N-FLPs. The calculations reveal that furan- and pyrrole-bridged P/N-FLPs can make CO₂ capture both thermodynamically and kinetically favorable (with activation energies of 5.4-7.7 kcal mol^-1 ) due to the aromatic stabilization of the transition states and products. Our findings could open an avenue to the design of novel FLPs for CO₂ capture.