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

For decades, N-2 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 N-2 activation and functionalization, highlighting a great potential of DLA for small molecule activation.

Automated summary

This study demonstrates the feasibility of metal-free activation of dinitrogen under mild conditions using a dual Lewis acid (DLA) through density functional theory (DFT) calculations. The DLA is also capable of activating a series of small molecules. The study highlights the importance of aromaticity in stabilizing intermediates and products. These findings provide an alternative approach to N-2 activation and functionalization, showcasing the potential of DLA for small molecule activation.