Abstract
Osmium(IV) dithioether complexes [OsLCl4][L = RS(CH2)2SR, RSCHCHSR, or o-C6H4(SR)2; R = Me or Ph] have been prepared from the ligands and sodium hexachloro-osmate(IV); [OsL′Br4](L′= MeS(CH2)2SMe or MeSCHCHSMe) are formed from K2[OsBr6]. Iridium(III) anions, [NMe4][IrLCl4], cis- and trans-[Ir(SMe2)2Cl4]–, [Ir(SPh2)2Cl4]–, and [Ir(SPh2)Cl5]2–, are oxidized by chlorine to the corresponding iridium(IV) complexes. Halogen oxidation of [PtLX2] produces [PtLX4](X = Cl or Br) and two unstable complexes [PtL″l4][L″= MeS(CH2)nSMe, n= 2 or 3]. Attempts to prepare thioether complexes of RuIV, RhIV, PdIV, CoIII, and NiIII have been unsuccessful. The isolated complexes have been characterized by i.r. and electronic spectroscopy, and where appropriate magnetic measurements and 1H n.m.r. spectroscopy. Variable-temperature 1H n.m.r. spectra show that inversion at sulphur co-ordinated to PtIV is more difficult than in the platinum(II) analogues. Thermal decomposition of [PtLX4](X = Cl, Br, or I) involves both dehalogenation and dealkylation.
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