Ammonia Formation Catalyzed by Dinitrogen‐Bridged Dirhenium Complex Bearing PNP‐Pincer Ligands under Mild Reaction Conditions
Ammonia Formation Catalyzed by Dinitrogen‐Bridged Dirhenium Complex Bearing PNP‐Pincer Ligands under Mild Reaction Conditions
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温和反应条件下二氮桥联铼配合物 PNP-Pincer 配体催化氨生成
DOI：
10.1002/anie.202102175
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Yoshizawa Kazunari
中科院分区：
文献类型：
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作者：
Nishibayashi Yoshiaki;Meng Fanqiang;Kuriyama Shogo;Tanaka Hiromasa;Egi Akihito;Yoshizawa Kazunari
以磷化氢配合物为前体，合成了一系列含吡啶基PNP型螯合体的铼配合物。以kc8为还原剂，以[HPCy3]BArF4（Cy=cyclohexyl, ArF=3,5‐（CF3）2C6H3）为质子源，在- 78℃的条件下，以催化剂铼原子为基础，二氮桥接的二氮配合物催化将二氮转化为氨。铼-二氮配合物还以kc8为还原剂，Me3SiCl为硅化剂，在环境反应条件下催化二氮的硅化反应，以催化剂的铼原子为基础得到11.7等量的三甲基硅胺。这些结果证明了在温和反应条件下使用铼-二氮配合物作为催化剂催化固氮的第一个成功例子。
A series of rhenium complexes bearing a pyridine‐based PNP‐type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen‐bridged dirhenium complex bearing the PNP‐type pincer ligands catalytically converts dinitrogen into ammonia during the reaction with KC8as a reductant and [HPCy3]BArF4(Cy=cyclohexyl, ArF=3,5‐(CF3)2C6H3) as a proton source at −78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium‐dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC8as a reductant and Me3SiCl as a silylating reagent under ambient reaction conditions to afford 11.7 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions using rhenium‐dinitrogen complexes as catalysts.