Rhenium‐Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide. (2nd December 2021)

• Record Type: Journal Article
• Authors: Alig, Lukas; Eisenlohr, Kim A.; Zelenkova, Yaroslava; Rosendahl, Sven; Herbst‐Irmer, Regine; Demeshko, Serhiy; Holthausen, Max C.; Schneider, Sven
• Is Part Of: Angewandte Chemie. Volume 134:Number 2(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-02
• Subjects: nitric oxide -- nitride -- nitrogen fixation -- nitrous oxide -- rhenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202113340
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : The coupling of (electro‐)chemically driven, reductive N2 splitting with nitrogen atom transfer to NO is reported. Nitrous oxide generation directly from dinitrogen and nitric oxide defines a new strategy for direct oxidative nitrogen fixation. Initial coordination of an activating NO ligand prepares the chemically robust Re V nitride for Re≡N/NO radical coupling.