Catalytic and structural studies of RhI complexes of (-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane. Asymmetric hydrogenation of acetophenonebenzylimine and acetophenone

J. Bakos, I. Tóth, B. Heil, G. Szalontai, L. Párkányi, V. Fülöp

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Abstract

Rhodium(I) complexes formed by (-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane (BDPP) are efficient catalysts for the hydrogenation of acetophenone and acetophenonebenzylimine. The composition of the solvent mixture and the reaction temperature have a marked influenced on the enantioselectivity. These effects are thought to be related to the enhanced conformational flexibility of six-membered rings when simple substrates without functional groups are coordinated to the rhodium. X-ray crystallographic studies reveal that in [Rh((S,S)-BDPP)NBD]+ (1) the ligand is in a chair conformation, and that in [Rh((S,S)-BDPP)COD]+ (2) the chelate ring is in a δ-skew conformation. Studies of Rh((S,S)-BDPP)(NBD)Cl (3) in solution indicate a trigonal bipyramidal structure with a chair conformation of the ring in aromatic solvents and a conformationally labile ring in methanol.

Original languageEnglish
Pages (from-to)263-276
Number of pages14
JournalJournal of Organometallic Chemistry
Volume370
Issue number1-3
DOIs
Publication statusPublished - Jul 11 1989

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ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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