Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes

Christoph Rüdinger, Holger Beruda, Hubert Schmidbaur

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Abstract

Disilylacetylene (1) has been obtained from LiA1H4 reduction of bis(trichlorosilyl)acetylene (2) and bis[(trifluoromethylsulfonyloxy)silyl]acetylene (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-l-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° in 15.

Original languageEnglish
Pages (from-to)1348-1360
Number of pages13
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume49
Issue number10
DOIs
StatePublished - 1 Oct 1994
Externally publishedYes

Keywords

  • Carbon Halogenated Silylolefines
  • Polysilylethenes
  • Silanes
  • Trichlorosilanes

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