Donor–Acceptor Stabilized Tetra(silanimine)

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• 作者：Yu-Liang Shan ; Bi-Xiang Leong ; Yongxin Li ; Rakesh Ganguly ; Cheuk-Wai So
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1609-1615
• 全文大小：441K
• ISSN：1520-510X

文摘

The synthesis of an oligo(silanimine) is described. The reaction of the amidinato silylene [LSiN(SiMe₃)₂] (1, L = PhC(NtBu)₂) with SiI₄ in toluene afforded a mixture of the silanimine [LSi(I)NSiI₃] (2), SiMe₃I, and Si₂I₆. The mechanistic studies showed that 1 reacts with SiI₄ to form the silyl ionic intermediate “{LSi(I)N(SiMe₃)₂}⁺{SiI₃}⁻”, which then eliminates SiMe₃I and “SiI₂” to form the silanimine intermediate “LSi(I)NSiMe₃”. It further undergoes a substitution with another molecule of SiI₄ to form a mixture of 2 and SiMe₃I. In addition, “SiI₂” undergoes an oxidative addition with SiI₄ to form Si₂I₆. Subsequently, compound 2 reacted with [LiN(SiMe₃)Ar] to form the silanimine [LSi(I)NSiI₂N(SiMe₃)Ar] (6, Ar = 2,6-iPr₂C₆H₃), which was then treated with KC₈ to give the donor–acceptor stabilized tetra(silanimine) [LSiN(SiMe₃)SiNAr]₂ (7). It comprises four formal silanimine “>Si═N-” units, which are linked together. Compounds 2, 6, and 7 were characterized by NMR spectroscopy and X-ray crystallography.