Predicting Small Molecule Activation including Catalytic Hydrogenation of Dinitrogen Promoted by a Dual Lewis Acid

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. Switching from the well‐developed strategy for activating dinitrogen by a frustrated Lewis acid pair (FLP), here we demonstrate a proof‐of‐concept study of a dual Lewis acid (DLA) to activate dinitrogen and a series of small molecules including carbon dioxide, formaldehyde, N‐ethylenemethylamine and acetonitrile via density functional theory calculations. In addition, by introducing a catalyst, the dinitrogen activation and hydrogenation could be accomplished in a thermodynamically and kinetically favorable fashion.