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.