Conversion of Dinitrogen into Nitrile: Cross-Metathesis of N2-Derived Molybdenum Nitride with Alkynes

被引：39

作者：

Song, Jinyi ^{[1
]}

Liao, Qian ^{[1
]}

Hong, Xin ^{[1
]}

Jin, Li ^{[1
]}

Mezailles, Nicolas ^{[2
]}

机构：

[1] Dalian Univ Technol, Zhang Dayu Sch Chem, 2 Linggong Rd, Dalian 116024, Liaoning, Peoples R China

[2] Univ Paul Sabatier, CNRS, Lab Heterochim Fondamentale & Appl, 118 Route Narbonne, F-31062 Toulouse, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 22期

基金：

中国国家自然科学基金;

关键词：

molybdenum– nitrido complexes; N-2; splitting; nitrile– alkyne cross-metathesis; nitriles; pincer ligands;

D O I：

10.1002/anie.202015183

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The direct synthesis of nitrile from N-2 under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N-2 into nitrile via a nitrile-alkyne cross-metathesis (NACM) process involving a N-2-derived Mo nitride. Treatment of the Mo nitride with alkyne in the presence of KOTf afforded an alkyne-coordinated nitride, which was then transformed into Mo-V carbyne and the corresponding nitrile upon 1 e(-) oxidation. Both aryl- and alkyl-substituted alkynes underwent this process smoothly. Experiments and DFT calculations have proved that the oxidation state of the Mo center plays a crucial role. This method does not rely on the nucleophilicity of the N-2-derived metal nitride, offering a novel strategy for N-2 fixation chemistry.

引用

页码：12242 / 12247

页数：6