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

Abstract

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 À 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, Nethylenemethylamine, 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.

Rational Design to Activate Tetrafluoromethane by Two-Coordinate Borinium

“…This process is driven by the restoration of the aromaticity of 6-P . Such an aromaticity-driven strategy has been widely applied to the activation of various small molecules, such as dinitrogen (N 2 ), − molecular hydrogen (H 2 ), carbon dioxide (CO 2 ), and carbon disulfide (CS 2 ), among others. A recent example of those is the activation of N 2 by borinium and bornium cations, which was reported by Zhu’s team .…”

Mechanistic study of nickel-catalyzed intramolecular [4 + 2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect

“…The activation of the C–C bond is very important in organic synthesis as it has great potential for the construction of complex molecules. 1 However, C–C bond cleavage has been a long-term challenge due to its kinetic inertia and thermodynamic stability. By releasing the inherent ring strain in compact ring structures, the ring-opening reaction becomes a powerful strategy to break strained C–C bonds.…”