Preparation and identification by proton nuclear magnetic resonance and proton–platinum-195 INDOR and vibrational spectroscopy of some platinum(II) complexes containing dimethyl sulphide as a bridging ligand

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Abstract
The anions [Pt2X6(SMe2)]2–(X = Cl and Br), in which SMe2 is the sole bridging group, and the anions [Pt2X5(SMe2)]– containing both a SMe2 bridge and a halide bridge have been characterised as their [Prn 4N] salts. Their 1H n.m.r. and vibrational spectra are reported and assigned. 1H N.m.r. and 1H {195Pt} INDOR spectroscopy are used to identify [Pt2Cl5(SMe2)2]– as a product of the reaction of [PPh4]Cl with Pt2Cl4(SMe2)2. The vibrational spectra of Pt2X4(SMe2)2(X = Cl or Br) are assigned on the basis of a sulphur-bridged structure but it is proposed that the analogous iodide is halide bridged. The sulphur-bridged anion [Pt2Cl5SMePh]– has been prepared but Pt2X4(SPh2)2 are halide bridged. Two cis-[PtCl2SMe2] groups linked by a single bridging SMe2 is postulated as the structure of Pt2Cl4(SMe2)3. Bands in the infrared spectrum of the benzene insoluble form of PtBr2(SMe2)2 are shown to be due to the impurity cis-PtBr2Me2SO·SMe2 rather than bridging SMe2. The significance of bridging dimethyl sulphide is discussed in the light of the chemical and spectroscopic results.

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