Systematic Design of a Frustrated Lewis Pair Containing Methyleneborane and Carbene for Dinitrogen Activation

Activation of atmospherically abundant dinitrogen (N-2) by metal-free species under mild reaction conditions has been one of the most challenging areas in chemistry for decades. Very recent but limited progress in N-2 activation by boron species, including two-coordinated borylene and methyleneborane and three-coordinated borole and borane, has been made toward metal-free N-2 activation. Here, we systematically probe an experimentally viable frustrated Lewis pair (FLP) containing two moieties (methyleneborane and carbene) for N-2 activation via density functional theory (DFT) calculations, which has proven to be an efficient approach for N-2 activation in a thermodynamically and kinetically favorable manner. Aromaticity is found to play a crucial role in stabilization of the product. This study could be a valuable alternative for the development of metal-free N-2 activation chemistry, highlighting great potential of FLP for N-2 activation and functionalization.