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

作　　者：崔海燕[1] 崔春明[2] 

机构地区：[1]南京农业大学理学院江苏省农药学重点实验室,南京210095 [2]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《有机化学》2016年第3期626-629,共4页Chinese Journal of Organic Chemistry

基　　金：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~~

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Me3Si Cl来制备硅亚胺的方法.合成了二胺基氯硅烷[Ar N(Si Me_3)]_2SiHCl(2)(Ar=2,6-i-Pr_2C_6H_3),通过~1H NMR,^(13)C NMR,^(29)Si 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(It Bu)和1,3-二异丙基-4,5-二甲基咪唑-2-亚基(Ii Pr)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(IMe_4)反应生成氢化硅亚胺3.Studies on the formation of silaimines are among the most fascinating topics in organosilicon chemistry. The first route to silaimine via eliminaition of Me_3 SiCl from diaminochlorosilanes is reported. Reaction of aminodichlorosilane Ar N（SiMe_3）SiHCl_2（1）（Ar=2,6-i-Pr_2C_6H_3） with ArN（SiMe_3）Li in Et_2O at-78 ℃ followed by stirring the mixture for 5 h at room temperature afforded diaminochlorosilane [Ar N（Si Me_3）]_2SiHCl（2）. Compound 2 has been fully characterized by ~1H NMR, ^（13）C NMR, ^（29）Si 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（It Bu） 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（IMe_4） 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 IMe_4 coordinate to 2 to form a hypervalent silicon species.

关 键 词：氯硅烷 氮杂环卡宾 硅亚胺 

分 类 号：O621.25[理学—有机化学]