含氮、硫配体钯、钌配合物的合成及其应用-化学专业论文.docxVIP

II II Abstract Syntheses of Palladium or Ruthenium Complexes with Nitrogen-/Sulfur-Containing Ligands and their Applications Syntheses of Palladium or Ruthenium Complexes with Nitrogen-/Sulfur-Containing Ligands and their Applications Abstract The Suzuki-Miyaura cross-coupling reaction is one of the most powerful and versatile methods to generate symmetric and unsymmetrical biaryls. However, these methods have some potential limitations because these cross-coupling reactions are often performed in organic solvents. We deliberately designed and synthesized sodium 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-1-yl)butane-1-sulfonate (NaL2) and 1-methyl-3-phenyl-1,3-dihydro-2H-imidazole-2-thione(L3), which could work well as auxiliary ligands to accelerate the Pd-catalyzed Suzuki-Miyaura coupling reactions. Reaction of 1H-imidazo[4,5-f][1,10]phenanthroline (L1) with one equiv. of 1,4-butane sultone a water-soluble bidentate nitrogen-containing ligand NaL2. Reaction of NaL2 and PdCl2 resulted in the formation of complex L2PdCl2, which demonstrated excellent catalytic activities towards the Suzuki-Miyaura cross-coupling reaction of arylboronic acid with aryl iodide or bromide or aryl dibromide in water. The catalytic system can also be reused several times. Reaction of PdCl2 with one equiv of 1-methyl-3-phenyl-1,3-dihydro-2H-imidazole-2-thione (L3), 1-methyl-3-(pyridin-2-yl)-1,3-dihydro-2H-imidazole-2-thione (L4) or 1,3-dimethyl-1,3-dihydro-2H-imidazole-2-thione (L5) yielded three complexes L3PdCl2 、 L4PdCl2 and L5PdCl2. L3PdCl2 displayed excellent reactivity for the Suzuki-Miyaura reactions reaction of arylboronic acid with aryl bromide. Reaction of 2-(1H-pyrazol-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (pzipH) and Ru(bpy)2Cl2 afforded one Ru(II) complex [Ru(bpy)2(Hpzip)](ClO4)2. [Ru(bpy)2(Hpzip)](ClO4)2 displayed high selectivity and sensitivity to Cu2+ and PPi with fluorescence turn-off in an aqueous solution or a CH3CN/H2O (9/1, v/v) solution, re