Interaction Between Ethynylsilanes and Transition-Metal-Complex

1.我们发现乙炔基硅烷与催化量的铑（I）络合物的反应以显著的区域和立体特异性进行，以高产率提供作为单一异构体的头对头偶联产物（E）-二硅烯炔。由此获得的烯炔上的甲硅烷基可以被其它有机基团取代。例如，用1当量的甲基锂处理二甲硅亚炔定量地得到乙炔锂。在催化量的甲醇钠存在下，二甲硅炔与甲醇反应，高产率地得到1，4-二甲硅基丁二烯.二乙炔基硅烷和二乙炔基二硅烷的类似反应分别得到聚[（亚甲硅烷基）丁烯炔-1，4-二基]和聚[（亚乙硅烷基）丁烯炔-1，4-二基]。由此获得的聚合物被发现是光活性的。用SbF_5蒸气处理由聚合物制备的固体薄膜，得到高导电薄膜，其电导率为0.0009- 1.09S/cm ~ 3。我们还研究了镍（0）络合物催化的2-芳基取代的（苯乙炔基）三硅烷的反应，并发现了新的异构化反应通过硅丙二烯-镍络合物形成，推测从1，3-甲硅烷基转移到乙炔碳原子。

1. We found that the reaction of ethynylsilanes with a catalytic amount of a rhodium (I) complex proceeds with remarkably regio-and stereospecificity to afford head-to-head coupling products, (E) -disilylenynes, as a single isomer in high yields. The silyl group on enynes thus obtained can be replaced by other organic groups. For example, treatment of the disilylenyne with 1 equiv of methyllithium gave a lithium acetylide quantitatively. Treatment of the disilylenyne with methanol in the presence of a catalytic amount of sodium methoxide gave a 1, 4-disilylbutadiene in high yield.2. Similar reaction of a diethynylsilane and diethynyldisilanes gave a poly [(silylene) butenyne-1, 4-diyl] and poly [(disilanylene) butenyne-1, 4-diyls], respectively. The polymers thus obtained were found to be photoactive. When the thin solid films prepared from the polymers were treated with SbF_5 vapor, highly conducting films were obtained whose conductivities were measured to be 0.0009-1.09 S/cm.3. We also investigated the nickel (0) -complex-catalyzed reaction of 2-aryl-substituted (phenylethynyl) trisilanes and found novel isomerization reactions via a silapropadiene-nickel complex formed presumably from a 1, 3-silyl shift to the ethynylic carbon atom.