Thiophenophanes and their coordination chemistry

This thesis describes studies of thiophenophane ligands and their coordination chemistry. In Chapter 1, aspects of macrocyclic thioether chemistry have been briefly reviewed. In Chapter 2, synthesis and characterization of eight thiophenophane ligands are described. The molecular structures of 2,5,8-trithia (9) (2,5)thiophenophane, 2,5,8,11-tetrathia (12) (2,5)thiophenophane and 2,5,9,13-tetrathia (13) (2,5)thiophenophane have been determined by X-ray methods. The effect of the rigid thiophene subunit with its two attached methylenes on the solid state conformations of the three macrocycles is discussed. In chapter 3, synthesis and properties of 15 copper(I) and (II) complexes of thiophenophane ligands and the open-chain ligand, 2,5-bis(2-hydroxyethylthiomethyl)thiophene, are described. The molecular structures of seven of these compounds are presented and spectral details are interpreted in the light of these structures. The redox properties of the complexes have been examined by cyclic voltammetry and the effect of solvent on their electrochemistry is discussed. In the first part of Chapter 4, synthesis and properties of palladium(II) and platinum(II) complexes of open-chain and macrocyclic thioether ligands are presented. The molecular structure of (PdBr...