Abstract
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.