(Ethyl‐, Ethenyl‐ and Ethynylsilyloxy)aluminum Compounds Generated by Heterolytic Cleavage of 1,3‐Disubstituted Disiloxanes

Peter Bissinger, Martin Paul, Jürgen Riede, Hubert Schmidbaur

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

sym‐Diorganodisiloxanes RH2SiOSiH2R (R = C2H5, 7; C2H3, 8; C2H, 9) are prepared by hydrolysis of organo(bromo)silanes which are available in high yields by the reaction of organo‐(phenyl)silanes with liquid HBr. Asymmetrical cleavage of these disiloxanes with AlCl3 leads to the formation of organo‐(chloro)silanes and aluminosiloxane dimers [RH2SiOAlCl2]2 (R = C2H5, 10; C2H3, 11; C2H, 12). Crystal structure determinations of 11 and 12 reveal a planar centrosymmetrical SiOAl2OSi skeleton with three‐coordinate oxygen atoms and tetrahedral four‐coordinate aluminum atoms. Treatment of 7–9 with Me2AlCl yields volatile dimethylaluminumorganosilyl oxides [RH2SiOAlMe2]x (R = C2H5, 13; C2H3, 14; C2H, 15; x = 2, 3, 4). NMR studies confirm the presence of more than one oligomer in solutions of these compounds. The asymmetrical compound (HC‐CSiH2O)2Me3Al2Cl (16), resulting from small amounts of MeAlCl2 in the Me2AlCl used, is isolated as a byproduct in the synthesis of 15. The crystal structure of 16 shows a disorder of the molecules leading to pseudosymmetry with a center of inversion.

Original languageEnglish
Pages (from-to)2579-2584
Number of pages6
JournalChemische Berichte
Volume126
Issue number12
DOIs
StatePublished - Dec 1993
Externally publishedYes

Keywords

  • 1,3‐Diorganodisiloxanes
  • Aluminosiloxanes
  • Siloxane cleavage by aluminium halides

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