New organopalladium building blocks for supramolecular chemistry

This thesis deals with the design, synthesis and characterization of some new metallosupramolecular molecules. These molecules are derived from the assembly of organopalladium building blocks and aromatic N-donor ligands.;Chapter Two describes the synthesis and characterization of building blocks with appended naphthyl groups and their use thereafter to produce supramolecular assemblies. Cyclometallation of the thioether ligand 1,3-bis(2-naphthylthiomethyl)benzene (NpS2) with [Pd(CH3CN4][BF4] 2 produced [Pd(NpS2)(CH3CN)][BF4]. The chloride adduct was also made to observe inversion of sulfur which was studied by variable temperature 1H NMR spectroscopy. The 1,2,4,5-tetrakis(naphthylthiomethyl)benzene (NpS4) ligand was synthesized and metallated to produce [Pd 2(NpS4)(CH3CN)2][BF4] 2. These building blocks were then used to make the assemblies of the Np-rod, Np-cleft, and the Np-box by using the ligands 4,4'-dipyridyl and 4,7-phenanthroline. All compounds were characterized through the use of 13C{1H} and 1H NMR spectroscopy as well as X-ray crystallography.;Chapter Three describes the design, synthesis and characterization of thioether ligands containing appended sulfonate groups. Direct palladation of these ligands in aqueous solution generates water-soluble organopalladium building blocks. These building blocks were characterized through the use of 13C{1H}and 1H NMR spectroscopy as well as X-ray crystallography.