Metal‐Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen. (7th December 2018)

• Record Type: Journal Article
• Authors: Schendzielorz, Florian; Finger, Markus; Abbenseth, Josh; Würtele, Christian; Krewald, Vera; Schneider, Sven
• Is Part Of: Angewandte Chemie. Volume 131:Number 3(2019)
• Page Start: 840
• Page End: 844
• Publication Date: 2018-12-07
• Subjects: Elektrochemie -- Photochemie -- Pincer-Liganden -- Rhenium -- Stickstoff-Fixierung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201812125
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N−N bond energy. Photochemical strategies that drive N2 fixation are scarcely developed. Here, the synthesis of a dinuclear N2 ‐bridged complex is presented upon reduction of a rhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2 H + /2 e − transfer of the pincer ligand. A three‐step cycle is demonstrated for N2 to nitrile fixation that relies on electrochemical reduction, photochemical N2 ‐splitting and thermal nitrogen transfer.