Exploring (Ph2PCH2CH2)2E ligand space (E = O, S, PPh) in RhI alkene complexes as potential hydroacylation catalysts

Sebastian D. Pike, Rebekah J. Pawley, Adrian B Chaplin, Amber L Thompson, Joel A. Hooper, Michael C. Willis, Andrew S Weller

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6 Citations (Scopus)

Abstract

The ligands (Ph2PCH2CH2)2E (E = O, S, PPh) have been used to form a variety of RhI cations [Rh{(Ph2PCH2CH2)2E}(alkene)] + (alkene = methyl acrylate, trimethylvinylsilane). Variable-temperature NMR spectroscopy shows that the methyl acrylate ligands undergo a fluxional process on the metal, via a 1-carbonyl intermediate, while the trimethylvinylsilane complexes cannot access this intermediate and do not undergo the same process. Their reactivity in hydroacylation reactions with 1-pentanal have been investigated, and these studies further suggest the important role that a chelating substituent next to the aldehyde might play in productive hydroacylation. A variety of Rh I cations [Rh{(Ph2PCH2CH2) 2E}(alkene)]+ (E = PPh, S, O; alkene = methyl acrylate and trimethylvinylsilane) have been prepared and their fluxional behaviour investigated by variable-temperature NMR spectroscopy.

Original languageEnglish
Pages (from-to)5558-5565
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2011
Issue number36
DOIs
Publication statusPublished - Dec 2011
Externally publishedYes

Keywords

  • Alkenes
  • Decarbonylation
  • NMR spectroscopy
  • Phosphanes
  • Rhodium

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