Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (<i>Z</i>)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry
R. Alan Aitken,
Graham Dawson,
Neil S. Keddie,
Helmut Kraus,
Heather L. Milton,
Alexandra M. Z. Slawin,
Joanne Wheatley,
J. Derek Woollins
Affiliations
R. Alan Aitken
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Graham Dawson
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Neil S. Keddie
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Helmut Kraus
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Heather L. Milton
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Alexandra M. Z. Slawin
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
Joanne Wheatley
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
J. Derek Woollins
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UK
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 (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 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.
