吡唑基喹啉配體之過渡金屬錯合物的合成與催化探討

Synthesis of Transition Metal Complexes Containing a Pyrazolyl Quinoline Ligand and Catalytic Activity Study

10.6342/NTU.2015.00096

吳采伶

鉗合配位基 ； 氧化裂解 ； 釕 ； 鈀 ； 鉑 ； pincer ligand ； oxidative cleavage ； ruthenium ； palladium ； platinum

國立臺灣大學化學系學位論文

2015年

碩士

劉緒宗

繁體中文

Complexation of 2‐pyrazolyl‐8‐hydroxyquinoline(4) with PdCl2 and PtCl2 afforded pincer complexes [(4)PdCl](5) and [(4)PtCl](7). The obtained complexes are stabilized through the chelation of the pincer ligand. The solubility of both complexes is poor. Replacement of chloride by acetonitrile through anion exchange gave complexes in ionic forms [(4)Pd(MeCN)]PF6(6) and [(4)Pt(MeCN)]PF6(8). The solubility of 6 and 8 improves quite a lot. Reaction of 4 with Ru(CO)3Cl2(THF) provided [(4)Ru(CO)2Cl](9). Complexes [(4)Ru(CO)2(MeCN)]PF6 (10) and [(4)Ru(CO)2(DMSO)]PF6(11) were formed by the replacement of chloride with acetonitrile and DMSO, respectively. Replacement of CO in complex 9 with DMSO provided complex [(4)Ru(CO)(DMSO)Cl](12). In all cases, ligand 4 acts as a N-N-O donor with two five-membered chelation rings. All complexes were characterized by NMR and mass analyses. Structures of complexes 6 and 9 were further confirmed by X ray crystallography and the geometry at the metal centers are square planar and octahedral, respectively. Complex 9 is able to act as a catalyst in the oxidation of C=C leading to the corresponding carboxylic acids with sodium periodate in a water/acetonitrile co-solvent system. This method is applicable toward both cycloalkenes and linear alkenes. Styrenes with electron donating substituents show higher activity. On the other hand, those with electron-withdrawing ones provide lower yields. Oxidative cleavage of 2-cyclohexenone proceeds smoothly with the decarboxylation to give glutaric acid as the product.

1. 鐘宏明(2016)。吡啶-喹啉酮配位基之鈀金屬錯合物的合成與催化探討。國立臺灣大學化學系學位論文。2016。1-143。