Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
Chemistry. 2018 Aug 6;24(44):11393-11401. doi: 10.1002/chem.201801517. Epub 2018 Jul 10.
The unexpected formations of fused polycyclic disilenes 2 a and (E),(Z)-3 b by the reduction of the 1,2-dibromodisilanes 5 a (R=Me) and 5 b (R=iPr) bearing bicyclo[1.1.1]pentasilanyl (BPS) groups is reported. The disilenes 2 a and (E),(Z)-3 b were characterized by a combination of NMR spectroscopy and X-ray diffraction analysis (XRD). The reduction of 5 b in the presence of 2,3-dimethyl-1,3-butadiene provided an ene adduct of the disilene 1 b bearing BPS groups, which suggested that an initial product of the reduction of 5 b was the disilene 1 b. Thermal reactions of 2 a and (E),(Z)-3 b afforded the highly strained saturated silicon clusters 4 a and 4 b. A computational study suggested that the transformation of 1 to 2, 3, or 4 can involve silyldisilene-disilanylsilylene rearrangement reactions and insertion reactions of a silylene into a Si-Si bond.
本文报道了通过还原带有双环[1.1.1]戊硅基（BPS）的 1,2-二溴二硅烷 5a（R=Me）和 5b（R=iPr）得到意想不到的融合多环二硅烯 2a 和（E），（Z）-3b。二硅烯 2a 和（E），（Z）-3b 通过 NMR 光谱和 X 射线衍射分析（XRD）相结合进行了表征。在 2,3-二甲基-1,3-丁二烯的存在下还原 5b 提供了带有 BPS 基团的二硅烯 1b 的烯加合物，这表明 5b 的还原的初始产物是二硅烯 1b。2a 和（E），（Z）-3b 的热反应得到了高度应变的饱和硅团簇 4a 和 4b。计算研究表明，1 到 2、3 或 4 的转化可能涉及硅二烯-二硅烷基硅烯重排反应和硅烯插入 Si-Si 键的反应。
