Rhenium‐Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide
Lukas Alig, Kim A. Eisenlohr, Yaroslava Zelenkova, Sven Rosendahl, Regine Herbst‐Irmer, Serhiy Demeshko, Max C. Holthausen, Sven Schneider
Abstract
Abstract Reductive splitting of N 2 is an attractive strategy towards nitrogen fixation beyond ammonia at ambient conditions. However, the resulting nitride complexes often suffer from thermodynamic overstabilization hampering functionalization. Furthermore, oxidative nitrogen atom transfer of N 2 derived nitrides remains unknown. We here report a Re IV pincer platform that mediates N 2 splitting upon chemical reduction or electrolysis with unprecedented yield. The N 2 derived Re V nitrides undergo facile nitrogen atom transfer to nitric oxide, giving nitrous oxide nearly quantitatively. Experimental and computational results indicate that outer‐sphere ReN/NO radical coupling is facilitated by the activation of the nitride via initial coordination of NO.