Hydroboration and Hydrosilylation of a Molybdenum?Nitride Complex Bearing a PNP-Type Pincer Ligand
Hydroboration and Hydrosilylation of a Molybdenum?Nitride Complex Bearing a PNP-Type Pincer Ligand
复制标题
带有 PNP 型钳形配体的钼氮化物配合物的硼氢化和氢化硅烷化
DOI：
10.1021/acs.organomet.1c00597
复制
发表时间：
2021
期刊：
影响因子：
2.8
通讯作者：
Nishibayashi Yoshiaki
中科院分区：
文献类型：
--
作者：
Itabashi Takayuki;Arashiba Kazuya;Tanaka Hiromasa;Yoshizawa Kazunari;Nishibayashi Yoshiaki
桥联氮与二氮桥联二钼络合物中的两个钼原子直接裂解生成的钼-氮化物与联苯基硼和二苯基硅烷的氢硼化和氢硅化反应分别得到相应的氢化硼-氢化物和氢化硅-氢化物络合物。密度泛函理论计算支持向钼-氮化物络合物的氢化硼化反应途径，从而得到相应的硼亚胺-氢化物络合物。钼-氮化物络合物与过量的儿茶酚硼烷在常压氮气中反应，在反应混合物水解后，得到高达2当量的以钼原子为基础的氨。这一结果表明，生成相应的硼胺的超化学计量反应是通过钼-氮化物络合物的氢硼化反应进行的。
Hydroboration and hydrosilylation of a molybdenum–nitride complex, prepared from the direct cleavage of the bridging dinitrogen coordinated to the two molybdenum atoms of a dinitrogen-bridged dimolybdenum complex, with pinacolborane and diphenylsilane give the corresponding borylimide–hydride and silylimide–hydride complexes, respectively. DFT calculations support a proposed reaction pathway of hydroboration toward the molybdenum–nitride complex to afford the corresponding borylimide–hydride complex. The reaction of the molybdenum–nitride complex with an excess amount of catecholborane under atmospheric nitrogen gas affords up to 2 equiv of ammonia based on the molybdenum atom after hydrolysis of the reaction mixture. This result indicates that a superstoichiometric reaction to afford the corresponding borylamine proceeds via hydroboration of a molybdenum–nitride complex as a key step.