Ammonia Synthesis at Room Temperature and Atmospheric Pressure from N(2): A Boron‐Radical Approach

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.