Interaction Between Ethynylsilanes and Transition-Metal-Complex

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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.