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 NN 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 pi* orbitals of dinitrogen is essential for its activation. Our findings suggest great potential of 7e boron radicals in the field of dinitrogen activation. A series of 7e boron radicals modelled by the experimentally synthesized ones are systematically studied towards N2 activation. The final formation of N2H2 is predicted via hydrogen transfer reactions.image