Manganese‐Catalyzed Ammonia Oxidation into Dinitrogen under Chemical or Electrochemical Conditions**
Hiroki Toda, Kaito Kuroki, Ryoichi Kanega, Shogo Kuriyama, Kazunari Nakajima, Yuichiro Himeda, Ken Sakata, Yoshiaki Nishibayashi
Abstract
Abstract Earth‐abundant metal‐catalyzed oxidative conversion of ammonia into dinitrogen is a promising process to utilize ammonia as a transportation fuel. Herein, we report the manganese‐catalyzed ammonia oxidation under chemical or electrochemical conditions using a manganese complex bearing ( 1S , 2S )‐ N , N′ ‐bis(3,5‐di‐ tert ‐butylsalicylidene)‐1,2‐cyclohexanediamine. Under chemical conditions using oxidant, up to 17.1 equivalents of N 2 per catalyst are generated. Also, mechanistic studies by stoichiometric reactions reveal that a nucleophilic attack of ammonia on manganese nitrogenous species occurs to form a nitrogen–nitrogen bond leading to dinitrogen. Moreover, we conduct density functional theory (DFT) calculations to confirm the plausible reaction mechanism. In addition, this reaction system is applicable under electrochemical conditions. The catalytic reaction proceeds with 96 % faradaic efficiency (FE) in bulk electrolysis to give up to 6.56 equivalents of N 2 per catalyst.