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Conversion of Dinitrogen into Nitrile: Cross‐Metathesis of N 2 ‐Derived Molybdenum Nitride with Alkynes
Author(s) -
Song Jinyi,
Liao Qian,
Hong Xin,
Jin Li,
Mézailles Nicolas
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202015183
Subject(s) - nitrile , alkyne , molybdenum , chemistry , nitride , carbyne , metathesis , nucleophile , aryl , combinatorial chemistry , alkyl , photochemistry , medicinal chemistry , organic chemistry , carbene , catalysis , polymer , layer (electronics) , polymerization
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.