路易斯碱稳定的氢化硅亚胺:二胺基氯硅烷与氮杂环卡宾的反应性研究

doi:10.6023/cjoc201511002

有机化学 ›› 2016, Vol. 36 ›› Issue (3): 626-629.DOI: 10.6023/cjoc201511002 上一篇下一篇

研究简报

路易斯碱稳定的氢化硅亚胺:二胺基氯硅烷与氮杂环卡宾的反应性研究

崔海燕^a, 崔春明^b

a 南京农业大学理学院江苏省农药学重点实验室南京 210095;
b 南开大学元素有机化学国家重点实验室天津 300071

收稿日期:2015-11-02 修回日期:2015-11-21 发布日期:2015-12-07
通讯作者: 崔海燕, 崔春明 E-mail:haiyancui555@163.com;cmcui@nankai.edu.cn
基金资助:
中央高校基本科研业务费(No. KJQN201551)、国家自然科学基金(No. 21402094)、江苏省科技计划项目(No. BK20140678)、国家重点基础研究发展规划(973计划, No. 2012CB821600)资助项目.

Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes

Cui Haiyan^a, Cui Chunming^b

a Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing 210095;
b State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071

Received:2015-11-02 Revised:2015-11-21 Published:2015-12-07
Supported by:
Project supported by the Fundamental Research Funds for the Central Universities (No. KJQN201551), the National Natural Science Foundation of China (No. 21402094), the Natural Science Foundation of Jiangsu Province (No. BK20140678), the National Key Basic Research Program of China (973 Program, No. 2012CB821600).

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摘要/Abstract

硅亚胺作为亚胺的重元素类似物, 是一类重要的含硅多重键化合物. 本研究首次报道了氮杂环卡宾诱导下二胺基氯硅烷脱除Me₃SiCl来制备硅亚胺的方法. 合成了二胺基氯硅烷[ArN(SiMe₃)]₂SiHCl (2) (Ar=2,6-i-Pr₂C₆H₃), 通过¹H NMR, ¹³C NMR, ²⁹Si NMR, 红外以及元素分析的表征确定了2的结构. 研究了2与不同位阻氮杂环卡宾的反应性, 发现其与位阻较大的1,3-二叔丁基咪唑-2-亚基(ItBu)和1,3-二异丙基-4,5-二甲基咪唑-2-亚基(IiPr)均不反应, 但是其与位阻较小的1,3,4,5-四甲基咪唑-2-亚基(IMe₄)反应生成氢化硅亚胺3.

关键词: 氯硅烷, 氮杂环卡宾, 硅亚胺

Studies on the formation of silaimines are among the most fascinating topics in organosilicon chemistry. The first route to silaimine via eliminaition of Me₃SiCl from diaminochlorosilanes is reported. Reaction of aminodichlorosilane ArN(SiMe₃)SiHCl₂ (1) (Ar=2,6-i-Pr₂C₆H₃) with ArN(SiMe₃)Li in Et₂O at -78 ℃ followed by stirring the mixture for 5 h at room temperature afforded diaminochlorosilane [ArN(SiMe₃)]₂SiHCl (2). Compound 2 has been fully characterized by ¹H NMR, ¹³C NMR, ²⁹Si NMR, IR and elemental analysis. Reactivity of 2 with different N-heterocyclic carbenes has been examined. It was found that 2 did not react with sterically hindered N-heterocyclic carbenes (NHC), 3-tert-butylimidazol-2-ylidene (ItBu) and 1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene (IiPr) at room temperature or under reflux conditions. However, compound 2 could react with one equivalent of 1,3,4,5-tetramethyl-imidazol-2-ylidene (IMe₄) to give base-stabilized 1-hydrosilaimine 3. Compound 3 can be viewed as the elimination product from 2 through loss of Me₃SiCl, as the small IMe₄ coordinate to 2 to form a hypervalent silicon species.

Key words: chlorosilanes, N-heterocyclic carbenes, silaimines

引用此文

崔海燕, 崔春明. 路易斯碱稳定的氢化硅亚胺:二胺基氯硅烷与氮杂环卡宾的反应性研究[J]. 有机化学, 2016, 36(3): 626-629.

Cui Haiyan, Cui Chunming. Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes[J]. Chin. J. Org. Chem., 2016, 36(3): 626-629.

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路易斯碱稳定的氢化硅亚胺:二胺基氯硅烷与氮杂环卡宾的反应性研究

Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes

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