Interaction Between Ethynylsilanes and Transition-Metal-Complex

1. 我们发现乙基硅烷与催化量的铑(I)配合物的反应具有显著的区域和立体专一性，以高收率提供头对头偶联产物(E) -二二甲苯作为单一异构体。由此得到的炔上的硅基可以被其他有机基团所取代。例如，用1等量的甲基锂处理二乙烯，定量得到乙酰化锂。在甲氧基钠催化量存在下用甲醇处理二二甲苯，得到高产的1,4 -二乙基丁二烯。二乙基硅烷和二乙基二硅烷的类似反应分别得到聚[（硅炔）丁烯- 1,4 -二基]和聚[（二硅炔）丁烯- 1,4 -二基]。由此得到的聚合物被发现具有光活性。经SbF_5蒸气处理后，得到了导电率为0.0009 ~ 1.09 S/cm.3的高导电薄膜。我们还研究了镍(0)络合物催化2-芳基取代（苯乙基）三硅烷的反应，并发现了新的异构化反应，可能是由1,3 -硅基转移到乙基碳原子形成的硅丙二烯-镍络合物。

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.