Achieving Control over the Reduction/Coupling Dichotomy of N 2 by Boron Metallomimetics.
Annalena GärtnerUhut S KaracaMaximilian RangMyron HeinzPhilipp D EngelIvo KrummenacherMerle ArrowsmithAlexander HermannAlexander MatlerAnna RempelRobert WitteHolger BraunschweigMax C HolthausenMarc-André LégaréPublished in: Journal of the American Chemical Society (2023)
We report a detailed computational and experimental study of the fixation and reductive coupling of dinitrogen with low-valent boron compounds. Consistent with our mechanistic findings, the selectivity toward nitrogen fixation or coupling can be controlled through either steric bulk or the reaction conditions, allowing for the on-demand synthesis of nitrogen chains. The electronic structure and intriguing magnetic properties of intermediates and products of the reaction of dinitrogen with borylenes are also elucidated using high-level computational approaches.