Trimethylsilylacetylene was catalytically dimerized by Ru(cod)(cot)/PR3 (cod = 1,5-cyclooctadiene, cot = cyclooctatriene) to give either Me3SiCH=C=C=CHSiMe3 when PR3 = PPh3 or (Z)-Me3SiCH=CH–C≡CSiMe3 when PR3 = PBun3, the latter being formed by stereoselective isomerization of initially formed (Z)-Me3SiCH=C=C=CHSiMe3.
1992polymerization processes, depolymerization processes polymerization processes, depolymerization processes O 0080
-091Regio-and Stereocontrolled Dimerization of tert-Butylacetylene to (Z)-1,4-Di-tert-butylbutatriene by Ruthenium Catalysis. Reaction Mechanism Involving Alkynyl-Vinylidene Coupling and Rearrangement of the Metal-Bound C4 Unit.-For the title reaction (I) → (II), a catalytic cycle is described which includes several important key steps such as ruthenium η2-alkyne to ruthenium vinylidene rearrangement, alkynylvinylidene coupling and isomerization of the resulting butenynyl moiety to the butatrienyl form. Many of the ruthenium model complexes are prepared. -(WAKATSUKI, Y.; YAMAZAKI, H.; KUMEGAWA, N.; SATOH, T.; SATOH, J. Y.; J. Am. Chem. Soc. 113 (1991) 25, 9604-9610; Inst. Phys. Chem. Res.,
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