Conversion of Dinitrogen into Acetonitrile under Ambient Conditions. (7th March 2016)

• Record Type: Journal Article
• Authors: Klopsch, Isabel; Kinauer, Markus; Finger, Markus; Würtele, Christian; Schneider, Sven
• Is Part Of: Angewandte Chemie. Volume 128:Number 15(2016)
• Page Start: 4864
• Page End: 4867
• Publication Date: 2016-03-07
• Subjects: Acetonitril -- Aktivierung kleiner Moleküle -- Pincer-Liganden -- Rhenium -- Stickstoff-Fixierung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201600790
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: About 20 % of the ammonia production is used as the chemical feedstock for nitrogen‐containing chemicals. However, while synthetic nitrogen fixation at ambient conditions has had some groundbreaking contributions in recent years, progress for the direct conversion of N2 into organic products remains limited and catalytic reactions are unknown. Herein, the rhenium‐mediated synthesis of acetonitrile using dinitrogen and ethyl triflate is presented. A synthetic cycle in three reaction steps with high individual isolated yields and recovery of the rhenium pincer starting complex is shown. The cycle comprises alkylation of a nitride that arises from N2 splitting and subsequent imido ligand centered oxidation to nitrile via a 1‐azavinylidene (ketimido) intermediate. Different synthetic strategies for intra‐ and intermolecular imido ligand oxidation and associated metal reduction were evaluated that rely on simple proton, electron, and hydrogen‐atom transfer steps. Abstract : CH3 C≡N aus N≡N : NH3 kann katalytisch aus N2 hergestellt werden, jedoch sind organische Produkte mit C‐N‐Bindungen nicht analog zugänglich, und selbst entsprechende stöchiometrische Prozesse wurden nur für wenige Beispiele berichtet. Hier wird eine rheniumvermittelte Acetonitrilsynthese bei Umgebungsbedingungen über N2 ‐Spaltung und ‐Alkylierung beschrieben, die als dreistufiger Kreisprozess eine Gesamtausbeute über 50 % liefert.