Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

被引：77

作者：

Schendzielorz, Florian ^{[1
]}

Finger, Markus ^{[1
]}

Abbenseth, Josh ^{[1
]}

Wuertele, Christian ^{[1
]}

Krewald, Vera ^{[2
]}

Schneider, Sven ^{[1
]}

机构：

[1] Georg August Univ, Inst Anorgan Chem, Tammannstr 4, D-37077 Gottingen, Germany

[2] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 03期

基金：

欧洲研究理事会;

关键词：

electrochemistry; nitrogen fixation; photochemistry; pincer ligands; rhenium; NITROGEN-FIXATION; CATALYTIC-REDUCTION; CLEAVAGE; N-2; AMMONIA; MOLYBDENUM; CONVERSION; COMPLEXES; RUTHENIUM; FUNCTIONALIZATION;

D O I：

10.1002/anie.201812125

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N-N bond energy. Photochemical strategies that drive N-2 fixation are scarcely developed. Here, the synthesis of a dinuclear N-2-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 N-2 to nitrile fixation that relies on electrochemical reduction, photochemical N-2-splitting and thermal nitrogen transfer.

引用

页码：830 / 834

页数：5