Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, Structure, Electrochemical Properties, and Reactivity.
Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, Structure, Electrochemical Properties, and Reactivity.
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四（二叔丁基甲基甲硅烷基）二锗烯：合成、结构、电化学性质和反应性。
DOI：
10.1002/hc.21165
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发表时间：
2014
影响因子：
0.3
通讯作者：
James Y. Becker
中科院分区：
文献类型：
--
作者：
Vladimir Ya. Lee;Kiera McNeice;Yuki Ito;Akira Sekiguchi;Natalie Geinik;James Y. Becker
以易得的1，1-二氯锗(TBu2MeSi)2GeCl2为原料，用石墨钾还原合成了四硅基取代的二氢呋喃(TBu2MeSi)2GeGe(SiMetBu2)21。化合物1是一个相当不寻常的二元体的例子，一方面在双键的Ge原子上具有平面几何结构，另一方面由于大体积的给予硅基取代基的电子和空间因素引起的异常扭曲的GeσGe键。尽管它在溶液中保持了其双键的结构完整性，1显示的反应活性不是>；GeGe<；键的特征，但在与亲核试剂(异氰化物、邻苯二酚)反应时，这是典型的>；Ge。与普通的烯烃不同，1通过循环伏安法产生稳定的阳离子和阴离子自由基。
The tetrasilyl‐substituted digermene (tBu2MeSi)2GeGe(SiMetBu2)21was prepared by the reduction of the readily available 1,1‐dichlorogermane (tBu2MeSi)2GeCl2with potassium graphite. Compound1is a rather unusual example of a digermene featuring planar geometry at the doubly bonded germanium atoms, on the one hand, and an extraordinarily twisted GeGe bond, on the other hand, caused by the electronic and steric factors of the bulky σ‐donating silyl substituents. Although it maintains the structural integrity of its double bond in solution,1revealed reactivity that is not characteristic of the >GeGe< bond but is typical for germylenes >Ge: upon reaction with nucleophilic reagents (isocyanide, orthoquinone). Unlike common alkenes,1affords stable cation and anion radicals generated by cyclic voltammetry.