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

doi:10.6023/cjoc201511002

Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (3): 626-629.DOI: 10.6023/cjoc201511002 Previous Articles Next Articles

Notes

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).

1. Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes.PDF(352KB)

Abstract

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

Cite this article

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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