带有庞大Eind基团的1,2-二卤二锗烯：合成、表征及向卤代锗烯类化合物的转化

1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids.

作者信息

Hayakawa Naoki, Sugahara Tomohiro, Numata Yasuyuki, Kawaai Hotaka, Yamatani Kenta, Nishimura Shogo, Goda Shun, Suzuki Yuko, Tanikawa Tomoharu, Nakai Hidetaka, Hashizume Daisuke, Sasamori Takahiro, Tokitoh Norihiro, Matsuo Tsukasa

机构信息

Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.

出版信息

Dalton Trans. 2018 Jan 15;47(3):814-822. doi: 10.1039/c7dt03819d.

DOI:10.1039/c7dt03819d

PMID:29250632

Abstract

1,2-Dihalodigermenes, (E)-(Eind)XGe[double bond, length as m-dash]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)Ge:, and GeX·dioxane in toluene via the cleavage and recombination of the Ge-C and Ge-X bonds. The dihalodigermenes have a Ge[double bond, length as m-dash]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)GeBr]. The bromogermylenoid can be isolated as a cryptand-separated potassium ion pair, [K(crypt-222)][(Eind)GeBr], which has been structurally characterized.

摘要

通过二芳基亚锗烯（Eind）Ge：与GeX·二氧六环在甲苯中发生配体再分布反应，经由锗 - 碳键和锗 - 卤键的断裂与重组，分离得到了带有稠环庞大Eind基团（Eind = 1,1,3,3,5,5,7,7 - 八乙基 - s - 氢化茚并四烯 - 4 - 基）的1,2 - 二卤代二锗烯（E）-（Eind）XGe═GeX（Eind）（X = Br和Cl），呈橙黄色晶体。这些二卤代二锗烯在晶体状态下具有Ge═Ge双键特征，但在溶液中会离解为卤代亚锗烯（Eind）XGe：。向溴代亚锗烯（Eind）BrGe：的四氢呋喃溶液中加入过量LiBr，会形成包含溴化锂锗烯醇盐[Li][（Eind）GeBr]的平衡混合物。该溴化锂锗烯醇盐可以作为穴状配体分离的钾离子对[K（crypt - 222）][（Eind）GeBr]被分离出来，并对其进行了结构表征。