Cleavage of Si-H, Si-C Bonds by Metal-Ligand Cooperation: Formation of Silyl Anion and Silylene Equivalents from Tertiary Silanes
Cleavage of Si-H, Si-C Bonds by Metal-Ligand Cooperation: Formation of Silyl Anion and Silylene Equivalents from Tertiary Silanes
复制标题
通过金属-配体合作断裂 Si-H、Si-C 键：从叔硅烷形成甲硅烷基阴离子和亚硅基等价物
DOI：
10.1021/acs.organomet.2c00037
复制
发表时间：
2022
期刊：
影响因子：
2.8
通讯作者：
K. Nozaki
中科院分区：
文献类型：
--
作者：
T. Higashi;S. Kusumoto;K. Nozaki
硅-氢键断裂生成含硅金属配合物在有机硅化合物的制备中起着至关重要的作用。本文报道了环烯酮铱配合物1与氢硅烷通过Si-H键的迁移反应得到羟基环烯酮铱硅基配合物4。在与烯丙基卤和丙烯酸乙酯的反应中证明了所得络合物中Ir-Si键的亲核性。此外，羟基硅铱配合物4通过还原消除硅中心的C-H键释放出苯而形成硅烯配合物。由三羧基硅烷合成的硅烯配合物表现出两亲性反应，这与硅烯的经典反应性一致。
The cleavage of silicon–hydrogen bonds to generate silicon-containing metal complexes has played an essential role in the preparation of organosilicon compounds. Herein, we report the reaction of cyclopentadienone iridium complex1with hydrosilanes to afford hydroxycyclopentadienyl iridium silyl complexes4via the umpolung of the Si–H bond. The nucleophilicity of the Ir–Si bond in the resulting complex was demonstrated in the reaction with an allyl halide and ethyl acrylate. Furthermore, a silylene complex was formed from hydroxycyclopentadienyl silyliridium complex4via the formal reductive elimination of the C–H bond at the silicon center to release benzene. The silylene complex synthesized from tricarbylsilane showed ambiphilic reactivities, which are consistent with the classical reactivities of silylenes.