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標題: | 多牙吡啶配位基及其雙金屬錯合物之合成與催化應用 Synthesis and Catalytic Application of Dimetal complex with 2,7-bis(2-pyridyl)-1,8-naphthyridine ligand |
作者: | Yung-Syuan Lan 藍詠萱 |
指導教授: | 劉緒宗(Shiuh-Tzung Liu) |
關鍵字: | 雙金屬錯合物,銅催化,烯胺, Dimetal complex,Copper-catalyzed,imine synthesis, |
出版年 : | 2012 |
學位: | 碩士 |
摘要: | 本篇論文利用四牙配位基2,7-bi(2-pyridyl)-1,8-naphthyridine (bpnp) 和過渡金屬(錳、銅、鈀)進行配位探討。而形成之雙銅金屬錯合物,進而利用作為苯胺與苯甲醇縮合形成烯胺之催化劑。
四牙氮配位基bpnp與MnCl2水合物反應,可得到單錳金屬錯合物[{Mn(bpnp)(OMe)Cl}2(μ-Cl)2]。單錳錯合物與[Cu2(CF3COO)4(CH3CN)2] 反應,發現銅金屬取代錳金屬,而形成雙銅金屬錯合物[Cu2(bpnp)(OH)Cl3] 。另外,在空氣下 bpnp與一價氧化銅在甲酸下反應,形成二價雙銅錯合物[Cu2(bpnp)(HCOO)3(OH)],由氫譜與X光單晶繞射分析可鑑定此分子,結構上雙銅皆為二價電子組態且以甲酸根和氫氧根為架橋配體。 雙銅錯合物[Cu2(bpnp)(HCOO)3(OH)] 可有效的作為苯甲醇類和胺類進行縮合反應之催化劑,得到高產率烯胺類產物。對於苯甲醇和胺類上不同電子和立體效應之取代基,均可以得到很好產率。相較於近年來的文獻使用較昂貴的鈀、銠、釕金屬當作催化劑應用於同類型之反應,價格低廉的銅金屬當作催化劑可大幅增加經濟效益。 This work involves the coordination study of a pyridinyl ligand 2,7-bis(2-pyridyl)-1,8-naphththyridine (bpnp) with various transition metal ions including Mn, Cu and Pd and catalytic activity of the resulting dicopper complex. Reaction of bpnp with [MnCl2] provided a mononuclear dimmer [{Mn(bpnp)(OMe)Cl2}(μ-Cl)2]. Such a manganese complex could undergo the metal exchange with Cu(II) ions to form a dinuclear species [Cu2(bpnp)(Cl)3(OH)]. Reaction of bpnp with Cu2O provided a dinuclear species [Cu2(bpnp)(HCOO)3(OH)]. These complexes were isolated and characterized by single-crystal X-ray crystallography. In the catalytic application, we developed a green one-pot synthesis of imines from amines and alcohols by using [Cu2(bpnp)(HCOO)3(OH)] as the catalyst. With the use of this catalyst, the direct synthesis of various imines from the corresponding amines and alcohols proceed smoothly under aerobic conditions in good to excellent yields. Noteworthy, the advantages of this method are the use of cheap cooper catalyst, solvent-free conditions, and the use of dioxygen as the oxidant. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/65031 |
全文授權: | 有償授權 |
顯示於系所單位: | 化學系 |
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