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

Abstract

AbstractReductive splitting of N2is 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 N2derived nitrides remains unknown. We here report a ReIVpincer platform that mediates N2splitting upon chemical reduction or electrolysis with unprecedented yield. The N2derived ReVnitrides 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.