A Unique Synthetic Route toward a 1,2‐Dihydrodigermene via Formal α‐Elimination of Bromo and Silyl Groups from a Bromo(phenylsilyl)germane

Daichi Uchida, Mariko Yukimoto, N. Tokitoh, Hiroko Yamada, Y. Mizuhata
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Abstract

A 1,2‐dihydrodigermene bearing Tbb {4‐t‐butyl‐1,3‐bis[bis(trimethylsilyl)methyl]phenyl} groups was successfully synthe­sized and isolated via formal α‐elimination of bromo and silyl groups from the corresponding Tbb‐substituted boromo(phenylsilyl)­germane. This novel synthetic method is conducted under mild conditions, representing a significant advantage in the field concerned. The synthesized 1,2‐dihydrodigermene was characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. In the 1H NMR spectrum, the Ge–H unit was found to be less electronically affected from the substituents compared to that of the previously reported 1,2‐dihydrodigermene. Moreover, the UV/vis spectra at various temperatures indicated the formation of the isomeric (dihydrogermyl)germylene. In fact, the 1,2‐dihydrodiger­mene once isolated reacted with DMAP in solution to afford the corresponding complex of the (dihydrogermyl)germylene.
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通过溴(苯基硅基)锗中溴基和硅基的正式 α-升华获得 1,2-二氢二锗烯的独特合成路线
通过从相应的 Tbb-取代硼代(苯基硅基)胚烷中正式α-消除溴基和硅基,成功合成并分离出一种带有 Tbb {4-叔丁基-1,3-双[双(三甲基硅基)甲基]苯基}基团的 1,2- 二氢二锗烯。这种新型合成方法在温和的条件下进行,在相关领域具有显著优势。合成的 1,2-二氢二锗烯通过核磁共振谱、质谱和单晶 X 射线晶体学进行了表征。在 1H NMR 光谱中发现,与之前报道的 1,2-二氢二锗烯相比,Ge-H 单元受取代基的电子影响较小。此外,在不同温度下的紫外/可见光谱显示形成了异构体(二氢二锗基)锗烯。事实上,1,2-二氢二锗一旦分离出来,就会与溶液中的 DMAP 发生反应,生成相应的(二氢二锗基)锗烯复合物。
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