Résumé
Ammonia, NH 3 , is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber–Bosch process, from the very stable dinitrogen molecule, N 2 and dihydrogen, H 2 . This process requires high temperatures and pressures, thereby generating ca 1.6 % of the global CO 2 emissions. Alternative strategies are needed to realize the functionalization of N 2 to NH 3 under mild conditions. Here, we show that boron‐centered radicals provide a means of activating N 2 at room temperature and atmospheric pressure whilst allowing a radical process to occur, leading to the production of borylamines. Subsequent hydrolysis released NH 4 + , the acidic form of NH 3 . EPR spectroscopy supported the intermediacy of radicals in the process, corroborated by DFT calculations, which rationalized the mechanism of the N 2 functionalization by R 2 B radicals.