Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
J Am Chem Soc. 2010 Jan 27;132(3):930-1. doi: 10.1021/ja910157h.
The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with diethylamine or diphenylamine produced the corresponding amino-substituted disilenes R(R'(2)N)Si=SiHR 2a, b (R = Si(i)PrCH(SiMe(3))(2), R' = Et (2a), Ph (2b)). The reaction of 1 with 9-borabicyclo[3.3.1]nonane afforded the boryl-substituted disilene R(R''(2)B)Si=SiHR 3 (R''(2)B = 9-borabicyclo[3.3.1]nonan-9-yl). Spectroscopic and X-ray crystallographic analyses of 2a, b, and 3 showed that 2a and 3 have a coplanar arrangement of the Si=Si double bond and amino or boryl groups, giving pi-conjugation between the Si=Si double bond and the lone pair on the nitrogen atom or vacant 2p orbital on the boron atom, whereas 2b exhibits no such conjugation.
1,1,4,4-四[双(三甲基甲硅烷基)甲基]-1,4-二异丙基四硅杂-2-炔 1 与二乙胺或二苯胺反应生成相应的氨基取代的二硅烯 R(R'(2)N)Si=SiHR 2a,b(R=Si(i)PrCH(SiMe(3))(2),R'=Et(2a),Ph(2b))。1 与 9-硼双环[3.3.1]壬烷反应得到硼取代的二硅烯 R(R''(2)B)Si=SiHR 3(R''(2)B=9-硼双环[3.3.1]壬烷-9-基)。2a、b 和 3 的光谱和 X 射线晶体学分析表明，2a 和 3 中 Si=Si 双键和氨基或硼基处于共面排列，使 Si=Si 双键和氮原子上的孤对电子或硼原子上的空 2p 轨道之间发生 pi 共轭，而 2b 则没有这种共轭。
