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

Ammonia, NH3, is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber–Bosch process, from the very stable dinitrogen molecule, N2 and dihydrogen, H2. This process requires high temperatures and pressures, thereby generating ca 1.6 % of the global CO2 emissions. Alternative strategies are needed to realize the functionalization of N2 to NH3 under mild conditions. Here, we show that boron‐centered radicals provide a means of activating N2 at room temperature and atmospheric pressure whilst allowing a radical process to occur, leading to the production of borylamines. Subsequent hydrolysis released NH4+, the acidic form of NH3. EPR spectroscopy supported the intermediacy of radicals in the process, corroborated by DFT calculations, which rationalized the mechanism of the N2 functionalization by R2B radicals. [ABSTRACT FROM AUTHOR]