Germabenzenylpotassium: A Germanium Analogue of a Phenyl Anion
Germabenzenylpotassium: A Germanium Analogue of a Phenyl Anion
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DOI：
10.1002/anie.201700801
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发表时间：
2017-04-10
影响因子：
16.6
通讯作者：
Tokitoh, Norihiro
中科院分区：
文献类型：
--
作者：
Mizuhata, Yoshiyuki;Fujimori, Shiori;Tokitoh, Norihiro
稳定的锗苯，1-Tbt-2-叔丁基-锗苯（Tbt = 2，4，6-三[双（三甲基甲硅烷基）甲基]苯基），与KC 8的还原导致形成2-叔丁基锗苯钾，即，苯基钾的锗类似物，同时消除Ge原子上的芳基。在惰性气氛下，这种锗苯钾可以以稳定的黄色晶体形式分离。在结晶状态下，以及在溶液中，germabenzenyl部分采用amonomeric形式，即使X-射线衍射分析表明存在高反应性Ge=C双键。的光谱和X-射线晶体学分析，结合理论计算表明这germabenzenyl阴离子的ambident字符，从芳香族和germylene共振结构的贡献。
Reduction of the stable germabenzene, 1-Tbt-2-tert-butyl-germabenzene (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl), with KC8 resulted in the formation of 2-tertbutylgermabenzenylpotassium, that is, the germanium analogue of phenylpotassium, under concomitant elimination of the aryl group from the Ge atom. Under an inert atmosphere, this germabenzenylpotassium could be isolated in the form of stable yellow crystals. In the crystalline state, as well as in solution, the germabenzenyl moiety adopts amonomeric form, even though the X-ray diffraction analysis suggests the presence of highly reactive Ge=C double bonds. The spectroscopic and X-ray crystallographic analyses, in combination with theoretical calculations indicate an ambident character for this germabenzenyl anion, with contributions from aromatic and germylene resonance structures.