PIO and IBO analysis to unravel the hidden details of the CO 2 sequestration mechanism of aromatically tempered N/B-based IFLPs.

Enhancing the catalytic reactivity of Frustrated Lewis Pairs (FLPs) in various activities such as CO 2 activation and sequestration has recently gained interest among researchers around the globe. A recent investigation showed the use of aromaticity as a tool to modulate the catalytic behaviour of FLPs, establishing a whole new dimension in this area. In this work, aromatically tempered N/B-based intramolecular frustrated Lewis Pairs (IFLPs) are proposed for CO 2 sequestration. Density functional theory (DFT)-based calculations were carried out to probe the reaction mechanism. The detailed mechanistic investigation was carried out using intrinsic reaction coordinate (IRC), principal interacting orbital (PIO), intrinsic bond orbital (IBO) and natural bonding orbital (NBO) analyses. The results show that aromatic gain in the system at the basic sites lowers the activation barrier, whereas the antiaromatic gain results in increased activation energy. The sequestration mechanism was found to be an asynchronous concerted mechanism, and polar solvents result in higher asynchronicity. This work, for the first time, reports asynchronicity in the catalytic behavior of aromatically tempered IFLPs, which can be crucial to designing better IFLPs for CO 2 sequestration.