Donor properties of sulphides. Part II. Complexes of rhodium(III) chloride with 1,4-thioxan and ligands of the type RSCH2CH2SR

Abstract

Rhodium(III) chloride reacts with 2,5-dithiahexane and 1,2-di(phenylthio)ethane to form complexes of the types [RhCl₃B]_n and [RhX₂B₂]⁺Y^–, where X = Cl or Br and Y = Cl, ClO₄,½S₂O₈, PF₆, or BPh₄. The complexes [RhCl₃B]_n are probably halogen-bridged dimers. The reactivity of several of these complexes has been investigated. The [RhCl₂B₂]⁺ cation, where B = 2,5-dithiahexane, has a trans- pseudo-octahedral configuration, and the isomerisation of the co-ordinated ligand molecules has been studied using far-infrared spectroscopy and proton magnetic resonance measurements. The significance of these results is discussed. The preparation and properties of the complexes cis-RhX₃(C₄H₈OS)₃, where X = Cl, Br, or I, are also described.