Ammonia Synthesis at Room Temperature and Atmospheric Pressure from N2: A Boron‐Radical Approach

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