1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene
1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene
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炔烃插入芳基溴甲锗烷的 Ge-C 键的 1,2-插入反应
DOI：
10.1039/d0dt01223h
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发表时间：
2020
影响因子：
4
通讯作者：
Tokitoh Norihiro
中科院分区：
文献类型：
--
作者：
Sugahara Tomohiro;Espinosa Ferao Arturo;Rey Planells Alicia;Guo Jing-Dong;Aoyama Shin;Igawa Kazunobu;Tomooka Katsuhiko;Sasamori Takahiro;Hashizume Daisuke;Nagase Shigeru;Tokitoh Norihiro
炔在二溴二烯的Ge-C键上的1,2-插入反应提供了稳定的溴基二烯晶体。与先前报道的lewis碱支持的乙烯基germylene相反，溴基germylene与3-己炔通过这种1,2插入反应得到的溴基germylene是一个无供体单体。根据实验观察结果结合理论计算，提出了一种可行的反应机理，认为[1+2]-环加合物和插入产物分别是动力学产物和热力学产物。
1,2-Insertion reactions of alkynes into the Ge–C bonds in dibromodigermenes afford stable crystalline bromovinylgermylenes. In contrast to previously reported Lewis-base-supported vinylgermylenes, the bromovinylgermylene obtained from reaction of the bromogermylene with 3-hexyne via such an 1,2-insertion is a donor-free monomer. A feasible reaction mechanism, proposed on the basis of the observed experimental results in combination with theoretical calculations, suggests that the [1+2]-cycloadduct and the insertion product are the kinetic and thermodynamic product, respectively.