1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids
1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids
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DOI：
10.1039/c7dt03819d
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发表时间：
2018-01-21
影响因子：
4
通讯作者：
Matsuo, Tsukasa
中科院分区：
文献类型：
--
作者：
Hayakawa, Naoki;Sugahara, Tomohiro;Matsuo, Tsukasa
1，2-二卤代二氢呋喃，(E)-(Eind)XGe-Gex(Eind)(X=Br和Cl)，含有稠环大体积eind基团(eind=1，1，3，3，5，5，7，7-八乙基-S-水合-4-基)，通过二芳基锗(Eind)(2)Ge：和GeX2中心点二恶烷在甲苯中的裂解和重组，通过Ge-C和Ge-X键的裂解和重组，分离出橙黄色晶体。二卤化锗在结晶态具有Ge=Ge双键特征，但在溶液中解离为卤化锗(Eind)XGe：。在溴锗的四氢呋喃溶液(Eind)BrGe：中加入过量的LiBr，形成了含有溴锗锂[Li+][(Eind)GeBr2](-)的平衡混合物。该溴胚烯类化合物可分离为一对钾离子对，[K+(cret-222)][(Eind)GeBr2](-)，其结构已得到表征。
1,2-Dihalodigermenes, (E)-(Eind)XGe-GeX(Eind) (X = Br and Cl), bearing the fused-ring bulky Eind group (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) have been isolated as orange-yellow crystals by the ligand redistribution reaction between the diarylgermylene, (Eind)(2)Ge:, and GeX2 center dot dioxane in toluene via the cleavage and recombination of the Ge-C and Ge-X bonds. The dihalodigermenes have a Ge=Ge double bond character in the crystalline state, but dissociate into halogermylenes, (Eind) XGe:, in solution. The addition of excess LiBr to the THF solution of the bromogermylene, (Eind)BrGe:, led to the formation of an equilibrium mixture containing the lithium bromogermylenoid, [Li+][(Eind)GeBr2](-). The bromogermylenoid can be isolated as a cryptand-separated potassium ion pair, [K+(crypt-222)][(Eind)GeBr2](-), which has been structurally characterized.