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 ReIV pincer platform that mediates N2 splitting upon chemical reduction or electrolysis with unprecedented yield. The N2 derived ReV 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.