Holzner Richard, Reiter Dominik, Frisch Philipp, Inoue Shigeyoshi
Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center Lichtenbergstraße 4 85748 Garching bei München Germany
RSC Adv. 2020 Jan 21;10(6):3402-3406. doi: 10.1039/c9ra10628f. eCollection 2020 Jan 16.
DMAP-stabilized silylenes 1a-c are obtained from the reductive debromination of the corresponding dibromosilanes in the presence of DMAP. Their distinctly different thermal isomerization reactions C-H bond activation, dearomative ring expansion and silyl migration are discussed. Furthermore, complexes 1 dissociate at elevated temperatures, providing the corresponding free silylenes , which are even capable of single-site activation of H. Additionally, a potassium-substituted silicon-centered radical 2 is isolated from overreduction of ( BuSi)SiBr.
在4-二甲氨基吡啶（DMAP）存在下，通过相应二溴硅烷的还原脱溴反应可得到由DMAP稳定的硅烯1a - c。文中讨论了它们明显不同的热异构化反应——碳氢键活化、去芳构化扩环反应和硅基迁移。此外，配合物1在高温下会解离，生成相应的游离硅烯，这些游离硅烯甚至能够实现氢的单中心活化。另外，通过（叔丁基硅基）硅溴的过度还原反应分离得到了一种钾取代的硅中心自由基2。
