Rhenium-Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide

Reductive splitting of N₂ 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 N₂ derived nitrides remains unknown. We here report a Re^IV pincer platform that mediates N₂ splitting upon chemical reduction or electrolysis with unprecedented yield. The N₂ 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.