Jin Da, Sun Xiaofei, Hinz Alexander, Roesky Peter W
Institute of Inorganic Chemistry (AOC), Karlsruhe Institute of Technology (KIT), Kaiserstr. 12, Karlsruhe 76131, Germany.
Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Kaiserstr. 12, Karlsruhe 76131, Germany.
Inorg Chem. 2024 Oct 7;63(40):18669-18675. doi: 10.1021/acs.inorgchem.4c02384. Epub 2024 Sep 25.
The reactivity of a mixed-valent silaiminyl-silylene [LSi-Si(NDipp)L] (L = PhC(NBu), Dipp = 2,6-Pr-CH) toward various substituted internal alkynes was investigated. In contrast to previous reports that primarily yield [Si(μ-C)Si]-modified rings via 1,2-addition of two silylenes in the center of the molecule, our study reveals a novel reaction pathway. The introduction of [R-C≡C-R] (R = Ph or SiMe, R = Ph or C≡CSiMe) gave unconventional insertion into one of the amidinate ligands, followed by migration of the {NBu} group to bridge two Si atoms. This results in the formation of diverse expanded silacycles.
研究了混合价态的硅亚胺基-硅烯[LSi-Si(NDipp)L]（L = PhC(NBu)，Dipp = 2,6-Pr-CH）对各种取代的内炔的反应活性。与之前主要通过分子中心两个硅烯的1,2-加成生成[Si(μ-C)Si]修饰环的报道不同，我们的研究揭示了一种新的反应途径。引入[R-C≡C-R]（R = Ph或SiMe，R = Ph或C≡CSiMe）会导致在其中一个脒基配体中发生非常规插入，随后{NBu}基团迁移以桥连两个硅原子。这导致形成了各种扩展的硅环。
