Screening seven-electron boron-centered radicals for dinitrogen activation

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 N₂ 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 N₂ 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.