Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (<i>Z</i>)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry.

Aitken, R Alan, Dawson, Graham ORCID: 0000-0002-1540-4791, Keddie, Neil S, Kraus, Helmut, Milton, Heather L, Slawin, Alexandra MZ, Wheatley, Joanne and Woollins, J Derek (2023) Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (<i>Z</i>)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry. Molecules (Basel, Switzerland), 29 (1). p. 221.

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Abstract

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the 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 (<i>Z</i>)-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 are 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.

Item Type:	Article
Uncontrolled Keywords:	X-ray structure, flash vacuum pyrolysis, hemilabile ligand, phosphine, phosphonium ylide, transition metal complex
Depositing User:	Symplectic Admin
Date Deposited:	28 Feb 2024 11:05
Last Modified:	28 Feb 2024 11:05
DOI:	10.3390/molecules29010221
Open Access URL:	https://doi.org/10.3390/molecules29010221
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3178961