Hydrolysis reaction of [Pt(NSO)2(PMe2Ph)2]. Crystal structures of [Pt(SO3)(PMe2Ph)3]·H2O and [{Pt(SO3)(PMe2Ph)2}2]·5CHCl3

The reaction of [Pt(NSO)2(PMe2Ph)2] with water in dichloromethane gives the compounds [Pt(SO3)(PMe2Ph)3]·H2O 1 and [{Pt(SO3)(PMe2Ph)2}2]·5CHCl32 which have been characterised by multielement NMR spectroscopy and X-ray crystallography. The mononuclear compound 1 has tetrahedrally distorted square-planar co-ordination of the platinum by three phosphines and the sulfur atom of the sulfite with trans angles of 160.4(1) and 161.2(1)°. The binuclear complex 2 contains a six-membered Pt2S2O2 ring in a chair conformation with each platinum being co-ordinated by two phosphines and a sulfur and oxygen atom of the different SO32– ligands. Phosphorus-31 NMR studies show that the reaction of Ag2SO3 with [PtCl2(PR3)2] gives 1 and 2 or simple, O,O′ complexes depending on the nature of PR3.