| This thesis describes the synthesis, characterization, complexation and subsequent reactivity studies of some acyclic, tridentate thioether ligands. The bonding analogy between thioethers and phosphines, and the usefulness of tris(phosphine) complexes, such as Rh(PPh{dollar}sb3)sb3{dollar}Cl,{dollar}sp{lcub}74{rcub}{dollar} leads to the hypothesis that a tris(thioether) coordination of platinum group metals might induce useful or unusual reactivity.; Three thioether ligands were synthesized: 3,7,11-trithiatridecane (TTTD); 1,9-diphenyl-1,5,9-trithianonane (DPTN) and 2,12-dimethyl-3,7,11-trithiatridecane (DMTT). The halide ligands of the platinum(II) complexes are readily abstracted, leaving a coordination site vacant which can be filled by various ancillary ligands such as PPh{dollar}sb3{dollar} or P(OMe){dollar}sb3{dollar}. Reaction of DPTN with (RhCl(COD)) {dollar}sb2{dollar} in the presence of Ag{dollar}sp+{dollar} formed the five coordinate complex (Rh(DPTN)(COD)) (BF{dollar}sb4{dollar}) and the reaction of DMTT with (IrCl(COE){dollar}sb2rbracksb2{dollar} in the presence of Ag{dollar}sp+{dollar} formed the five coordinate complex (Ir(DMTT)(COE){dollar}sb2{dollar}) (BF{dollar}sb4{dollar}). The {dollar}etasp4{dollar}-COD ligand in (Rh(DPTN)(COD)) (BF{dollar}sb4{dollar}) was inert to substitution by other Lewis base ligands, while one of the {dollar}etasp2{dollar}-COE ligands in (Ir(DMTT)(COE){dollar}sb2{dollar}) (BF{dollar}sb4{dollar}) can be replaced with either CO or PPh{dollar}sb3{dollar}. (Abstract shortened by UMI.)... |
