- [2σ + 2σ + 2π]-Cycloaddition of quadricyclane to partially methylated chlorosilylalkenes
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[2σ + 2σ + 2π]-Cycloaddition of quadricyclane to trissilylated ethenes Cl3 - nMenSiCH=CSiMenCl3 - n(SiMe3 - nCln) (n = 1, 2) at 95 °C affords 3,3,4-trissilylated exo-tricyclo[4.2.1.02,5]non-7-enes. Tetrakis(trichlorosilyl)ethene does not react with quadricyclane.
- Chapala, Pavel P.,Bermeshev, Maxim V.,Lakhtin, Valentin G.,Genaev, Alexander M.,Tavtorkin, Alexander N.,Finkelshtein, Eugene Sh.
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- Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes
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Disilylacetylene (1) has been obtained from LiAlH4 reduction of bis(trichlorosilyl)acetylene (2) and bisacetylene (4).The catalytic hydrosilylation of 2 with HSiCl3 affords tris(trichlorosilyl)ethene (5) and 1,1,2-tris(trichlorosilyl)ethane (6).The synthesis of 6, trans-bis(trichlorosilyl)ethene (8) and 1,1-bis(trichlorosilyl)ethene (9) has been accomplished by hydrosilylation of trichlorosilylacetylene (7) which was synthesized by the reaction of trichloro(trifluoromethylsulfonyloxy)silane with sodium acetylide.Reductive elimination of halogen from 1,1,1,2-tetrachloro-bis(trichlorosilyl)ethane (10) and 1,2-dibromo-1,1-bis(trichlorosilyl)ethane (13) gave the corresponding ethenes 1,1-dichloro-bis-(trichlorosilyl)ethene (11), trichloro-trichlorosilylethene (12), 1,1-bis(trichlorosilyl)ethene (9) and 1-chloro-2,2-bis(trichlorosilyl)ethene (14).Tetrakis(trichlorosilyl)ethene (15) has been obtained in a three step synthesis starting from chloromethyl-trichlorosilane or dichloromethyl-trichlorosilane.By LiAlH4 reduction of trichlorosilylethenes under various reaction conditions, the silylethenes trans-dichloro-di(silyl)ethene (16), 1,1-dichloro-di(silyl)ethene (17), trichloro-silylethene (18), 1-bromo-1-silylethene (19), trans-di(silyl)ethene (20), 1-chloro-2,2-di(silyl)ethene (21), tri(silyl)ethene (22), and 1,1,2-tri(silyl)ethane (23) could be generated.Silylethyne and silyl-chloroethyne were identified as side products.The crystal and molecular structures of 2, 5 and 15 have been determined by single crystal X-ray diffraction. 2 and 5 crystallize from the melt in the monoclinic space groups Cc and P21/n, respectively. 15 has been crystallized by sublimation (orthorhombic, space group Pbca). 5 and 15 feature strongly distorted ethene skeletons with a double bond twist of 28.1 deg in 15. - Keywords: Silanes, Trichlorosilanes, Polysilylethenes, Carbon Halogenated Silylolefines
- Ruedinger, Christoph,Beruda, Holger,Schmidbaur, Hubert
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p. 1348 - 1360
(2007/10/02)
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