- 學位論文
合成與鑑定多功能銅、鈀錯合物
Synthesis and Characterizations of Multifunctional Copper and Palladium Complexes
摘要
鑒於自然的永續發展，將環境中小分子活化並利用或儲存，一直是科學上的重大議題。然而，過程中面臨的問題，例如過高的活化能以及多電子與質子轉移過程，都使反應效率受限。故其中催化劑的設計就扮演了重要的角色。 別於以往以金屬原子為反應中心且配位基不參與反應之錯合物，本篇論文同時引入了金屬-配位基協同作用(metal-ligand cooperation)及金屬-金屬協同作用(metal-metal cooperation)。藉由多金屬之構型可預期錯合物具備多電子轉移能力；同時配位基具備可活化之質子，可藉由該質子的轉移改變錯合物之反應性，以利錯合物在較溫和之環境下反應。基於上述概念，在設計結構上使用了phathalazine作為有機骨架，並以具備酸性質子的磷基側臂，合成多金屬錯合物。 在完成配位基的合成與鑑定後，將配位基分別與具不同陰離子之銅一價鹽類反應，可分別得到具不同陰離子且不同構型之雙銅錯合物，該類錯合物於大氣下展現了良好的穩定性。經過結構鑑定後，以循環伏安法測量其氧化還原電位，並以紫外-可見光光譜法測量其光物理性質，探討其應用於發光材料的可能性；同時也將此系列雙銅錯合物應用於耦合反應催化以及二氧化碳的電催化還原反應。除此之外，也討論了銅二價鹽類的金屬錯合反應，與其產物鑑定。 同時，鑑於鈀金屬的高催化活性，本篇論文也利用了PdCl2與配位基進行錯合。以X光繞射晶體法鑑定產物後將此三核心鈀錯合物應用於催化Suzuki耦合反應，以比較與其他鈀催化劑之反應性差異。
並列摘要
In view of the sustainability of nature, it is a big issue to transfer small molecules of surrounding into beneficial feedstocks. However, either high energy barriers or kinetic barriers of electron and proton transfer processes may limit the efficiency, so it is challenging to design a suitable catalyst toward such reactions. Different from previous organometallic catalysts, in which reactions merely took place at metal centers, we simultaneously introduce Metal-Metal Cooperation and Metal-Metal cooperation in our complex design. We expect the interaction between metal centers through the multi-metallic structure and the deprotonation of acidic protons on the ligand may influence the reactivity of complexes toward catalytic reactions. Based on the concepts mentioned above, we design a phathalazine-based PNNP pincer ligand with the existing of acidic protons on the phosphine-based sidearms. After synthesizing the ligand, we get a series of di-copper(I) complexes with different structures through the metalation with different copper(I) salts. Besides, the copper(I) complexes show unusual stability in the air. We also use cyclic voltammetry to measure the redox properties of complexes. In the aspect of application, we try to utilize the complexes as luminescent materials, and also test the reactivity of complexes toward coupling reaction and electrocatalytic CO2 reduction reaction. Meanwhile, we find the formation of similar copper(I) complexes from the metalation with copper(II) salts while the detail mechanism is still in process. Additionally, in view of the catalytic reactivity of palladium, we use PdCl2 to do the metalation with ligand and get a three-centered palladium complex. We compare its reactivity with reported literature toward Suzuki coupling reaction.