Just Published in Journal of the American Chemical Society05/23/2023
Achieving Control over the Reduction/Coupling Dichotomy of N2 by Boron Metallomimetics
Authors: Annalena Gärtner, Uhut S. Karaca, Maximilian Rang, Myron Heinz, Philipp D. Engel, Ivo Krummenacher, Merle Arrowsmith, Alexander Hermann, Alexander Matler, Anna Rempel, Robert Witte, Holger Braunschweig*, Max C. Holthausen*, and Marc-André Légaré*
Abstract: 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.