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

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: Cui Haiyan, Cui Chunming,
Received Date: 2 November 2015
Available Online: 21 November 2015
Fund Project: 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)

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.
- chlorosilanes,
- N-heterocyclic carbenes,
- silaimines
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