理學院: 化學研究所指導教授: 劉緒宗邱暉勝Chiu, Hui-HsengHui-HsengChiu2017-03-022018-07-102017-03-022018-07-102016http://ntur.lib.ntu.edu.tw//handle/246246/272119摘要 本研究主要涵蓋重氮雙牙配位基 (E)-4-(pyridin-2-yldiazenyl)phenol (4) 及 (E)-2-(phenyldiazenyl)pyridine (5) 的合成，以及探討其與 Ru(II) 和 Pd(II) 之配位化學。所合成出許多鈀金屬錯合物有 [(4)PdCl2] (4aa)、[(4)Pd(TFA)2] (4ab)、[(4)Pd(CH3)Cl] (4b)、[(5)PdCl2] (5a) 及 [(2-(2’-hydroxy-arylazo)pyridine)PdCl] (5b); 與含三聯吡啶之釕金屬錯合物 [(2)(terpyridine)RuCl] (4d)。這些錯合物可由NMR、ESI-MASS及FAB-MASS確認其結構，其中錯合物4aa、4b及4d更進一步以X光單晶繞射分析儀解析確認。配位基4上具有羥基酸性基團，利用紫外光分析儀探討pH值改變對錯合物所造成的影響。 在催化探討上，選用Suzuki耦合反應來比較這一系列鈀金屬錯合物在催化活性上的不同，以及不同取代基對此反應速率的差異，進而探討其反應機制。利用鹼性環境下配位基去質子化之特性使其溶於水中，使其在水相中仍維持其催化活性，進而實現綠色化學的理念。In this work, bidentate azo-contained ligand (E)-4-(pyridin-2-yldiazenyl)phenol (4) and (E)-2-(phenyldiazenyl)pyridine (5) were synthesized. Complexes containing these ligands including [(4)PdCl2] (4aa)、[(4)Pd(TFA)2] (4ab)、[(4)Pd(CH3)Cl] (4b)、[(5)PdCl2] (5a)、[(2-(2’-hydroxy-arylazo)pyridine)PdCl] (5b) and [(4)(terpyridine)RuCl] (4d) were prepared. Complex 4aa、4b and 4d have been characterized by NMR,ESI-MASS,FAB-MASS and X-ray crystallography. Because of the characteristic of hygroxy group, the use of UV-Vis analyzer investigate influence of pH changes caused by complexes. Discussion on catalysis, the choice of Suzuki coupling reaction to compare this series of palladium metal complexes differ in catalytic activity, as well as various substituents reacted rate differences, and then explore the reaction mechanism. Deprotoned ligand in the base environment can enhance the solubility in water. So that it maintains its catalytic activity in the aqueous phase, realizing the concept of green chemistry.8032093 bytesapplication/pdf論文公開時間: 2021/4/15論文使用權限: 同意有償授權(權利金給回饋學校)鈀金屬釕金屬PalladiumRutheniumthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/272119/1/ntu-105-R02223159-1.pdf