Li Siqi, Huang Zhipeng, Liu Huifang, Liu Meijiang, Zhang Chaofeng, Wang Feng
Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, China.
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Dalton Trans. 2022 Jan 25;51(4):1553-1560. doi: 10.1039/d1dt03107d.
We herein present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and hydrazine over an iron-molybdenum sulfide catalyst ([FeMo]S). The heterogeneous hydrogen transfer reduction can be efficiently carried out at 30 °C and provides anilines with 95-99% selectivities. The gas product analysis demonstrates that [FeMo]S can catalyze the decomposition of NH to H* species, not H. Combining with the kinetic analysis of the aniline generation rates from nitrobenzene and intermediates, the nitro group reduction to the nitroso group is confirmed to be the rate-determining step. The positive slope of Hammett's equation suggests that the critical intermediate in the rate-determining step is in the negative state, which suggests that the active H* should be in polar states (H and H). These findings will provide a novel route for the synthesis of substituted anilines and broaden the application of MoS catalysts under mild conditions.
我们在此展示了一种在铁钼硫化物催化剂（[FeMo]S）上由硝基芳烃和肼化学选择性合成芳胺的有效方法。非均相氢转移还原反应能在30°C下高效进行，生成的苯胺选择性达95 - 99%。气体产物分析表明，[FeMo]S可催化NH分解为H物种，而非H。结合由硝基苯和中间体生成苯胺速率的动力学分析，证实硝基还原为亚硝基是速率决定步骤。哈米特方程的正斜率表明，速率决定步骤中的关键中间体呈负电性，这意味着活性H应处于极性状态（H⁺和H⁻）。这些发现将为取代苯胺的合成提供一条新途径，并拓宽MoS催化剂在温和条件下的应用范围。
