Intramolecular rearrangements of sulphines co-ordinated to Pt involving insertion and reductive coupling reactions. X-Ray crystal and molecular structure of (E)-[PtII(PhS)(PPh3)2(PhSCSO)]·C6H6, a new type of heterocumulene–metal complex

Abstract

The Pt⁰(PPh₃)₂-unit in [Pt⁰(PPh₃)₂(XYCSO)](X = Y =S-aryl or X =S-alkyl, Y = aryl, both stereoisomers), in which the sulphine XYCSO is η²-CS co-ordinated, inserts into a C–S bond yielding an equilibrium mixture consisting of two stereoisomers (E)- and (Z)-[Pt^IIX(PPh₃)₂(YCSO)] and varying amounts of [Pt⁰(PPh₃)₂(XYCSO)], depending on the geometry of the co-ordinated sulphine.