Synthesis and Reduction of Octasilyl[4]radialene. Structure and Dynamic Study of [4]Radialene Dianion with Eight-Center Ten-Electron π-System
Synthesis and Reduction of Octasilyl[4]radialene. Structure and Dynamic Study of [4]Radialene Dianion with Eight-Center Ten-Electron π-System
复制标题
八硅基[4]辐射烯的合成与还原以及八中心十电子π体系[4]辐射烯双阴离子的动力学研究。
DOI：
10.1246/bcsj.71.1705
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发表时间：
1998
影响因子：
4
通讯作者：
H. Sakurai
中科院分区：
文献类型：
--
作者：
Tsukasa Matsuo;A. Sekiguchi;M. Ichinohe;K. Ebata;H. Sakurai
3,3,5,5,8,8,10,10,13,13,15,15,18,18,20,20-hexadecamethyl-3,5,8,10,13,15,18,20-octasilacycloicosa-1,6,11,16-tetrayne (1) 与三摩尔量的分子内反应[Mn(CO)3(Me-Cp)]在THF中在光化学和回流条件下产生八甲硅基[4]辐射烯衍生物(2)。 2 与碱金属（Li、Na 和 K）在 THF 中反应，得到相应二价阴离子 (4) 的二碱金属盐，具有八中心十电子 π 体系。八甲硅基[4]辐射二烯二阴离子(4a)的二锂盐的分子结构已通过X射线晶体学确定。两个锂原子位于上下，并与轴烯骨架的原子键合，形成双-CIP结构。讨论了 4a 的结构参数与 2 的比较。还根据 NMR 波谱数据讨论了溶液中 4a 的结构。 4a 的两个 Li+ 离子并未固定在甲苯-d8 中的 π-骨架上，而是流动的，从而在...上形成对称结构（bis-CIP）。
The intramolecular reaction of 3,3,5,5,8,8,10,10,13,13,15,15,18,18,20,20-hexadecamethyl-3,5,8,10,13,15,18,20-octasilacycloicosa-1,6,11,16-tetrayne (1) with three molar amounts of [Mn(CO)3(Me-Cp)] in THF under photochemical and refluxing conditions produced octasilyl[4]radialene derivative (2). The reaction of 2 with alkali metals (Li, Na, and K) in THF gave dialkali metal salts of the corresponding dianion (4) with an eight-center ten-electron π-system. The molecular structure of dilithium salt of octasilyl[4]radialene dianion (4a) has been established by X-ray crystallography. The two lithium atoms are located above and below and are bonded to the atoms of the radialene framework to give a bis-CIP structure. The structural parameters of 4a are discussed in comparison to those of 2. The structure of 4a in solution has also been discussed on the basis of NMR spectroscopic data. The two Li+ ions of 4a are not fixed to the π-skeleton in toluene-d8, but are fluxional, giving a symmetric structure (bis-CIP) on...