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

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.