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.

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.