Meng Fanqiang, Kuriyama Shogo, Tanaka Hiromasa, Egi Akihito, Yoshizawa Kazunari, Nishibayashi Yoshiaki
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
School of Liberal Arts and Sciences, Daido University, Minami-ku, Nagoya, 457-8530, Japan.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):13906-13912. doi: 10.1002/anie.202102175. Epub 2021 May 10.
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 KC as a reductant and [HPCy ]BAr (Cy=cyclohexyl, Ar =3,5-(CF ) C H ) 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 KC as a reductant and Me SiCl 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.
一系列带有吡啶基PNP型钳形配体的铼配合物由磷化铼配合物作为前体合成。一种带有PNP型钳形配体的双氮桥连二铼配合物，在以KC作为还原剂、[HPCy]BAr（Cy = 环己基，Ar = 3,5-(CF)CH）作为质子源的反应中，于 -78°C下催化将双氮转化为氨，基于催化剂的铼原子可得到8.4当量的氨。该铼 - 双氮配合物在与KC作为还原剂、MeSiCl作为硅烷化试剂的反应中，在环境反应条件下也催化双氮的硅烷化反应，基于催化剂的铼原子可得到11.7当量的三（三甲基硅基）胺。这些结果证明了使用铼 - 双氮配合物作为催化剂在温和反应条件下催化固氮的首个成功实例。
