Syntheses, Structures And Properties Of Palladium Sulfobenzoate Complexes

Nowadays, coordination polymers have attracted much attention because of their multiple structures and novel functions. This thesis focuses on synthetic routes, structural studies and characterization of palladium sulfobenzoate complexes. We used palladium salts, sulfobenzoate and N-donor neutral ligands as raw materials and14palladium sulfobenzoate complexes have been synthesized. All these complexes have been characterized by X-ray single crystal structure analysis and IR. And seven of them have been further characterized by elemental analysis, thermo gravimetric analysis, UV-vis, fluorescence and XRD. In addition, these seven complexes have been investigated as catalysts in MPS (methyl phenyl sulfide) oxygenation reaction. With different structures and properties of these complexes, this thesis mainly divided into the following four aspects to discuss.1. Five palladium2-sb complexes with phen have been obtained:[Pd(phen)2]-2(2-Hsb)(1),[pd(phen)2]-2(2-Hsb).2H2O(2),[Pd(phen)2]-[Pd(phen)(2-sb)2]·6H2O (3),2[Pd(phen)2]·4(2-Hsb)·8H2O(4),[Pd(phen)(2-sb)(H2O)]·2H2O (5). Complexes1,2and4are cation-anion species with2-Hsb ligands partly deprotonated in the structures. In complexes3and5, the carboxy group in2-sb has coordinated with the palladium atom and the sulfobenzoate has been fully deprotonated. Complexes1,2and3have been characterized by IR, elemental analysis, thermo gravimetric analysis, UV-vis, fluorescence and catalytic oxygenation reaction investigation. Complex3, which acts as homogeneous catalysts, displays more satisfactory efficiency in MPS oxygenation reaction than the other two cation-anion complexes. As some literatures reports, with acid added to the catalytic reaction, an obvious enhance in catalytic efficiency will be observed. So we added little2-H2sb as acid into the reaction and the catalytic efficiency has been improved as expected.2. Two palladium3-sb complexes with phen have been synthesized: [Pd(phen)2](3-sb)·3H2O (6),[Pd(phen)(NH3)2]·(3-sb)·3H2O (7). They both are cation-anion species with the counter ion3-sb2-in the structure. Both two complexes have been characterized by IR, elemental analysis, thermo gravimetric analysis, UV-vis, fluorescence, XRD and catalytic oxygenation reaction investigation.3. Four palladium2-sb complexes with Hdpa have been synthesized:[Pd(2-Hsb)2(Hdpa)2]·2H2O(8),[Pd(Hdpa)2]2(2-Hsb)(9),[Pd(Hdpa)2][2-sb(CH3)]2(10),[Pd(Hdpa)2]·Cl2·2H2O (11). The2-sb has coordinated with palladium atom in complex8and there are many hydrogen bonds in complex8. These intermolecular hydrogen bonds extended the structures to a2-D architecture. Complexes9,10and11are cation-anion species. In complex9,2-Hsb-ligand is partly deprotonated and acts as a counter ion in the structure. In complex10, the2-sb has esterized with the solvent CH3OH and the product ester acts as a counter ion in the structure. In complex11, there is no2-sb ligand in the structure and the Cl" acts as a counter ion in the structure.4. In the process of synthesis, there are some interesting solvent reaction happened, and4complexes have been obtained. They are [Pd(Hdpa)2][2-sb(CH3)]2(10),[Pd(2,2’-bipy)](CN)2(12),[Pd(L)2]·2(2-msb)(L=8-amino-nitrogen naphthalene)(13),[Pd(CH3C(NH)-NH-(NH)CCH3)2]2·2(2-sb)·2H2O (14). We have analyzed their synthetic method, structure and IR.