Screening seven‐electron boron‐centered radicals for dinitrogen activation

Abstract The activation of dinitrogen is significant as nitrogen‐containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO‐LUMO gap (10.8 eV) and high bond dissociation energy (945 kJ mol −1 ) renders its activation under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate that a series of seven‐electron (7e) boron‐centered radical can be used to activate N 2 via density functional theory calculations. It is found that boron‐centered radicals containing amine ligand perform best on the thermodynamics of dinitrogen activation. In addition, when electron‐donating groups are introduced at the boron atom, these radicals can be used to activate N 2 with low reaction barriers. Further analysis suggests that the electron transfer from the boron atom to the π* orbitals of dinitrogen is essential for its activation. Our findings suggest great potential of 7e boron radicals in the field of dinitrogen activation.