Wagner–Meerwein-Type Rearrangements of Germapolysilanes - A Stable Ion Study

The rearrangement of tris­(trimethylsilyl)­silyl­trimethylgermane 1 to give tetrakis­(trimethylsilyl)­germane 2 was investigated as a typical example for Lewis acid catalyzed Wagner–Meerwein-type rearrangements of polysilanes and polygermasilanes. Direct 29Si NMR spectroscopic evidence is provided for several cationic intermediates during the reaction. The identity of these species was verified by independent synthesis and NMR characterization, and their transformation was followed by NMR spectroscopy.

本研究以三(三甲基硅基)硅基三甲基锗（化合物1）重排生成四(三甲基硅基)锗（化合物2）作为典型案例，系统探究了路易斯酸（Lewis acid）催化的聚硅烷与聚锗硅烷的瓦格纳-米尔魏因（Wagner–Meerwein）型重排反应。本工作通过硅-29（²⁹Si）核磁共振波谱法，为该反应过程中形成的多种阳离子中间体提供了直接的光谱证据。通过独立合成与核磁共振波谱表征确证了这些中间体的结构，并借助核磁共振波谱追踪了其转化历程。