The reactivity of a mixed-valent silaiminyl-silylene [LSi–Si(NDipp)L] (L = PhC(N^tBu)₂, Dipp = 2,6-ⁱPr-C₆H₃) toward various substituted internal alkynes was investigated. In contrast to previous reports that primarily yield [Si(μ-C₂)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 [R₁–C≡C–R₂] (R₁ = Ph or SiMe₃, R₂ = Ph or C≡CSiMe₃) gave unconventional insertion into one of the amidinate ligands, followed by migration of the {N^tBu} group to bridge two Si atoms. This results in the formation of diverse expanded silacycles.

中文翻译：

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内部炔烃非常规插入混合价硅氨基-亚硅基


研究了混合价硅胺基-亚甲硅基 [LSi–Si(NDipp)L] (L = PhC(N ^t Bu) ₂ , Dipp = 2,6-Pr-C ₆ H ₃ ) 对各种取代内炔的反应性。与之前的报道主要通过分子中心两个硅烯的 1,2-加成反应生成 [Si(μ-C ₂ )Si] 修饰环相比，我们的研究揭示了一种新的反应途径。引入 [R ₁ –C≡C–R ₂ ]（R ₁ = Ph 或 SiMe ₃ ，R ₂ = Ph 或 C≡CSiMe ₃ ），以非常规的方式插入脒配体之一，然后迁移 {N ^t Bu}基团桥接两个Si原子。这导致了多种扩展硅环的形成。