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

引用本文: 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. doi: 10.6023/cjoc201511002 shu

Citation: Cui Haiyan, Cui Chunming. Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes[J]. Chinese Journal of Organic Chemistry, 2016, 36(3): 626-629. doi: 10.6023/cjoc201511002 shu

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,
,}

1.
a 南京农业大学理学院江苏省农药学重点实验室南京 210095;
2.
b 南开大学元素有机化学国家重点实验室天津 300071

通讯作者: 崔海燕, 崔春明; 崔海燕, 崔春明

基金项目:
中央高校基本科研业务费(No. KJQN201551) (No. KJQN201551)

国家自然科学基金(No. 21402094) (No. 21402094)

江苏省科技计划项目(No. BK20140678) (No. BK20140678)

国家重点基础研究发展规划(973计划, No. 2012CB821600)资助项目. (973计划, No. 2012CB821600)

摘要: 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

English

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

Cui Haiyan ^{a,
,} ,
Cui Chunming ^{b,
,}

1.
a Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing 210095;
2.
b State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071

Corresponding author: 崔海燕, 崔春明; 崔海燕, 崔春明

Received Date: 02 November 2015
Available Online: 07 December 2015
Fund Project:
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.

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:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

通讯作者: 崔海燕, 崔春明; 崔海燕, 崔春明

English

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

Corresponding author: 崔海燕, 崔春明; 崔海燕, 崔春明

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

通讯作者: 崔海燕, 崔春明; 崔海燕, 崔春明

English

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

Corresponding author: 崔海燕, 崔春明; 崔海燕, 崔春明

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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