Macrocylic thioether-esters and thioether-thioesters and their palladium, platinum and silver complexes

Abstract

Preparations by the high dilution method are reported for seven macrocyclic thioether-esters and thioether-thioesters (L1–;L7). Yields in these reactions between thiodiglycolyl dichloride and appropriate α,ω-diols or dithiols range from 10 to 51%. The compounds are characterized by 1H and 13C NMR, IR and high resolution mass spectroscopy. They react with salts of Pd(II), Pt(II) and Ag(I) to form complexes of which MX 2·L2, (M = Pt, X = Cl; M = Pd, X = Cl, Br, I, SCN), [Pd(L2) 2][CF 3SO 3] 2·H 2O and [Ag(L5) 2][CF 3SO 3]·C 2H 5OH have been isolated and characterized by elemental analysis, IR and NMR spectroscopy. NMR spectra indicate reversible dissociation of the ligand occurs in dimethyl sulfoxide solvent for PdCl 2·L2 but not for the Pt analogue. For PtCl 2·L2, spectra indicate that the ligand is undergoing a conformational ‘wag’ about its pair of equivalent sulfurs. These remain bound to the metal while the unique sulfur moves from the apical position of the coordination sphere to a non-coordinated situation. Simultaneously, inversions at the bound sulfurs are occurring.