Activation of atmospherically abundant dinitrogen (N2) 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 N2 activation by boron species, including two-coordinated borylene and methyleneborane and three-coordinated borole and borane, has been made toward metal-free N2 activation. Here, we systematically probe an experimentally viable frustrated Lewis pair (FLP) containing two moieties (methyleneborane and carbene) for N2 activation via density functional theory (DFT) calculations, which has proven to be an efficient approach for N2 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 N2 activation chemistry, highlighting great potential of FLP for N2 activation and functionalization.

https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03520