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For decades, N2 activation and functionalization have required the use of transition metal complexes. Thus, it is one of the most challenging projects to activate the abundant dinitrogen through metal‐free systems under mild conditions. Here, we demonstrate a proof‐of‐concept study on the catalytic hydrogenation of dinitrogen (with activation energy as low as 15.3 kcal mol−1) initiated by a dual Lewis acid (DLA) via density functional theory (DFT) calculations. In addition, such a DLA could be also used to activate a series of small molecules including carbon dioxide, formaldehyde, N‐ethylenemethylamine, and acetonitrile. It is found that aromaticity plays an important role in stabilizing intermediates and products. Our findings provide an alternative approach to N2 activation and functionalization, highlighting a great potential of DLA for small molecule activation. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]