Thermal rearrangement of thiocarbonyl-stabilised triphenylphosphonium ylides leading to (Z)-1-diphenylphosphino-2-(phenylsulfenyl)alkenes and their coordination chemistry

R Alan Aitken*, Graham Dawson, Neil Steven Keddie, Helmut Kraus, Heather Lindsay Milton, Alexandra Martha Zoya Slawin, Joanne Wheatley, J Derek Woollins

*Corresponding author for this work

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Abstract

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these have been characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus.
Original languageEnglish
Article number221
Number of pages13
JournalMolecules
Volume29
Issue number1
DOIs
Publication statusPublished - 31 Dec 2023

Keywords

  • Flash vacuum pyrolysis
  • Phosphonium ylide
  • Phosphine
  • Hemilabile ligand
  • Transition metal complex
  • X-ray structure

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