Ferrocenylmethylphosphanes and the Alpha Process for Methoxycarbonylation: The Original Story

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  • Kevin M. Fortune
  • Christa Castel
    University of Liverpool
  • Craig M. Robertson
    University of Liverpool
  • Peter N. Horton
    University of Southampton
  • Mark E. Light
    University of Southampton
  • Simon J. Coles
    University of Southampton
  • Mark Waugh
    Mitsubishi Chemical UK Limited
  • William Clegg
    Newcastle University
  • Ross W. Harrington
    Newcastle University
  • Ian R. Butler
The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours.
Original languageEnglish
Article number57
JournalInorganics
Volume9
Issue number7
DOIs
Publication statusPublished - 17 Jul 2021

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