Syntheses, Structures, and Properties of Tricyclo[5.1.1.13,5]tetrasilachalcogenanes (Thex2Si2E2)E2 (E = S, Se) and Tricyclo[5.1.1.13,5]tetragermachalcogenanes (Thex2Ge2E2)E2 (E = S, Se)
Syntheses, Structures, and Properties of Tricyclo[5.1.1.13,5]tetrasilachalcogenanes (Thex2Si2E2)E2 (E = S, Se) and Tricyclo[5.1.1.13,5]tetragermachalcogenanes (Thex2Ge2E2)E2 (E = S, Se)
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三环[5.1.1.13,5]四硅硫属烃烷 (Thex2Si2E2)E2 (E = S, Se) 和三环[5.1.1.13,5]四甲硫属烃烷 (Thex2Ge2E2)E2 (E = S, Se) 的合成、结构和性质
DOI：
10.1021/om970432r
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发表时间：
1997
期刊：
影响因子：
2.8
通讯作者：
H. Matsumoto
中科院分区：
文献类型：
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作者：
M. Unno;Yuuki Kawai;Hiroaki Shioyama;H. Matsumoto
在四氢呋喃中，ThexSiCl3(Thex=1，1，2-三甲基丙基)与Li2S和Li2Se在室温下反应，分别得到三环[5.1.1.13，5]四硅醇烷(Thex2Si2S2)S2(1)和(Thex2Si2Se2)Se2(2)。ThexGeCl3与Li2S和Li2Se发生类似的反应，分别得到三环[5.1.1.13，5]四锗醇(Thex2Ge2S2)S2(3)和(Thex2Ge2Se2)Se2(4)。1-−-4的X-射线结晶学分析表明，这些分子是类质同晶的，具有应变的“双层”结构(坎迪亚尼结构)。化合物1和3在190℃下分别异构化为金刚烷类体系：三环[3.3.1.13，7]四硅硫烷(5)和三环[3.3.1.13，7]四锗硫烷(6)。对于4，金刚烷笼的异构化发生在低得多的温度(如80℃)，这表明Ge−Se双层笼比Si−S笼和Ge−S笼具有更高的活性。
Reactions of ThexSiCl3 (Thex = 1,1,2-trimethylpropyl) with Li2S and Li2Se in tetrahydrofuran at room temperature afforded the tricyclo[5.1.1.13,5]tetrasilachalcogenanes (Thex2Si2S2)S2 (1) and (Thex2Si2Se2)Se2 (2), respectively. Similar reactions of ThexGeCl3 with Li2S and Li2Se gave the tricyclo[5.1.1.13,5]tetragermachalcogenanes (Thex2Ge2S2)S2 (3) and (Thex2Ge2Se2)Se2 (4), respectively. X-ray crystallography of 1−4 reveals that these molecules were isomorphous and possess strained “double-decker”-like frameworks (Candiani structure). Compounds 1 and 3 show isomerization at 190 °C to the adamantane-like systems, tricyclo[3.3.1.13,7]tetrasilathiane (5) and tricyclo[3.3.1.13,7]tetragermathiane (6), respectively. For 4, isomerization to the adamantane cage takes place at much lower temperature (e.g., 80 °C), indicating that Ge−Se double-decker-like cage is more reactive than Si−S and Ge−S cages.