多芽1,8-萘啶配基及其雙金屬錯合物與催化應用

Multidentate 1,8-Naphthyridine Ligand and Its Dinuclear Complexes Catalytic Application

唐維鴻(Wei-Hung Tang)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6342/NTU.2013.00253

摘要

中文摘要
論文的主要內容為合成2,7-di(2,2′-dipyridylamino)-1,8-naphthyridine (4)的多芽1,8-萘啶配基以及其銅和釕雙金屬錯合物，進而利用雙釕金屬錯合物作為鄰苯二胺環化加成反應的催化劑應用。
將2,7-dichloro-1,8-naphthyridine (3)與2,2′-dipyridylamine進行碳氮鍵耦合反應，可合成擁有更多的配位基團的化合物4。使用 [(η6-p-cymene)RuCl2]2與化合物4進行配位可得到雙核釕金屬錯合物 [(4)Ru2(η6-p-cymene)2(Cl)2(PF6)2] (5a)。另外化合物4亦可以分別與 [Cu(CH3CN)4PF6]、CuI和CuBr進行配位可分別得到雙核銅金屬錯合物 [(4)2Cu2(THF)2(PF6)4] (5b)、[(4)Cu2I2] (5c)及[(4)Cu2Br2] (5d);藉由X光單晶繞射分析儀器鑑定，顯示釕金屬錯合物 (5a)為六配位的形態存在，銅二價金屬錯合物 (5b)為五配位的形態存在。銅一價金屬錯合物 (5c)及(5d)可藉由ESI-MASS質譜分析鑑定結構，為四配位的形態存在，由碘或溴組成架橋基連結兩金屬核。
在催化應用探討上，測試雙釕金屬錯合物 5a對於鄰苯二胺環化加成反應的活性。發現於鹼性條件下，錯合物 5a在氧氣作為氧化劑，可有效將鄰苯二胺與乙二醇、乙醇胺反應，得到產率不錯的quinoxaline。相較於其他釕金屬前驅物，雙核釕金屬錯合物 5a的活性，推測可能有金屬之間協同作用使然。

關鍵字

萘啶配基及其雙金屬錯合物

並列摘要

Abstract
We have successfully prepared a multidentate ligand 2,7-di(2,2′-dipyridylamino) -1,8-naphthyridine (4), and its ruthenium dinuclear complexes.
The use of the prepared ruthenium complex as the catalyst for the cycloaddition of o-phenylenediamine with ethyleneglycol was investigated.
For the ligand synthesis, the coupling reaction of C-N bond between 2,7-di- chloro-1,8-naphthyridine (3) and 2,2′-dipyridylamine yielded 4, which has six coordination sites for the metal. Coordination of 4 with [(η6-p-cymene)RuCl2]2、[Cu(CH3CN)4PF6]、 CuI and CuBr resulted in a dinuclear ruthenium and dicopper complexes [(4)Ru2(η6-p-cymene)2(Cl)2(PF6)2] (5a)、[(4)2Cu2(THF)2(PF6)4] (5b)、 [(4)Cu2I2] (5c) and [(4)Cu2Br2] (5d), respectively. Complexes of 5a and 5b were characterized by X-ray crystals. We had found that 5a is a hexa-coordination complex, and 5b is a five-coordination complex. Complex 5c and 5d were characterized by ESI-MASS. Complexes 5c and 5d are four-coordination complexes with iodine and bromine as the bridging ligand, respectively.
In the catalytic application, tests of the dinuclear ruthenium complex (5a) as catalyst for the cycloaddition reaction of o-phenylenediamine with ethyleneglycol were performed. With oxygen as the oxidant, reaction of o-phenylenediamine with ethylene glycol and ethanolamine with the use of 5a as the catalyst afforded the corresponding quinoxaline in good yields.

並列關鍵字

1,8-Naphthyridine Ligand and Its Dinuclear Complexes

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