Phosphine containing carbosilane dendrimers based on polyhedral silsesquioxane cores as ligands for hydroformylation reaction of oct-1-ene

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Abstract

Radical additions of diethyl- and diphenylphosphine have been used to prepare 1st and 2nd generation dendrimers based on polyhedral oligosilsesquioxane cores by a divergent synthetic method. The 1st generation dendrimer is built on either 16 and 24 vinyl or allyl arms formed by successive hydrosilation and vinylation or allylation of vinyl-functionalised polyhedral silsesquioxanes. Successive hydrosilation/allylation followed by hydrosilation/vinylation and addition of phosphine produce the 2nd generation dendrimer. The dendrimers have been used as ligands for the hydrofornlylation of oct-1-ene catalysed by [Rh(acac)(CO)(2)]. Using the alkylphosphine-containing dendrimers as ligands, alcohols (nonan-1-ol and 2-methyloctanol) are obtained, whilst the diphenylphosphine counterparts lead to the formation of aldehydes (nonan-1-al and 2-methyloctanal). Linear to branched ratios of 3/1 are obtained for the diethylphosphine compounds while ratios of 12 to 14/1 are given by the diphenylphosphine dendritic molecules. (C) 2002 Published by Elsevier Science B.V.

Original languageEnglish
Pages (from-to)99-105
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Volume182/183
Publication statusPublished - 31 May 2002

Keywords

  • silsesquioxane
  • dendrimer
  • hydroformylation
  • rhodium
  • phosphine
  • RHODIUM-CATALYZED HYDROFORMYLATION
  • PHOSPHORUS-CONTAINING DENDRIMERS
  • ASYMMETRIC CATALYSIS
  • MEMBRANE REACTOR
  • COMPLEXES
  • HYDROCARBONYLATION

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