雙同碳膦烷碳烯的鈀金屬鉗型錯合物之合成及其在薗頭偶合反應之應用

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姓名

蔡欣言(Hsin-Yen Tsai) 查詢紙本館藏

畢業系所

化學學系

論文名稱

雙同碳膦烷碳烯的鈀金屬鉗型錯合物之合成及其在薗頭偶合反應之應用
(Synthesis of Bis(carbophosphinocarbene) Palladium Pincer Complex and its application to Sonogashira Coupling Reaction)

相關論文

★ 雙芽手性卡本金屬錯合物之合成與結構鑑定及其在催化反應之應用

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摘要(中)

卡本的中心碳具有兩對孤對電子對，相比碳烯是一種強的電子予體，擁有良好的親核力能與金屬配位。三種子分類中的同碳雙膦烷(carbodiphosphorane, CDP) 以及同碳雙碳烯 (carbodicarbene, CDC) 作為配位基或是生成之金屬錯合物，於催化反應中已有相當程度的發展；至於同碳膦烷碳烯(carbophosphinocarbene, CPC) 雖在文獻中已被報導，相較兩者卻缺乏相關的研究。在本論文中我們以2,6-雙二苯基膦吡啶為骨架連接兩個同碳膦烷碳烯，形成之鉗型配位基具有C-N-C三牙基，與雙吡啶二氯化鈀反應可以成功得到鉗型鈀金屬錯合物。此設計利用σ供電子能力的同碳膦烷碳烯作為鉗型配體兩側，用以提升整體結構穩定性，進而預期能有好的催化活性。後續發現此鈀催化劑能夠進行無銅薗頭偶合催化反應，即使置換不同的烷基或芳基溴與末端炔反應，也能成功生成碳碳鍵的偶聯產物。藉由此研究可以得知雙同碳膦烷碳烯的鈀錯合物具有不錯的催化能力，未來具有應用於其他催化反應之潛力。

摘要(英)

The central carbon of carbones (CL2) bears two lone electron pairs. Due to the two lone pairs on the central carbon, carbones have been regarded as ligand with both  and -donation. This property enables carbones acting as an electron-rich ligand for metallic complexes. In the past few year, the carbodiphosphoranes (CDPs) and carbodicarbenes (CDCs) have been developed to ligate metallic complexes for catalytic application. Carbophosphinocarbenes (CPCs) has been reported recently, but there is still lack of relevant research pertaining coordination chemistry and applications in catalysis. This thesis uses the skeleton of 2,6-bis(diphenylphosphino)pyridine to connect two carbone units which form pincer-type ligand with C-N-C tridentate coordination site. We successfully obtain pincer bis(carbone) palladium complex by reacting free pincer bis(carbone) ligand with bis(pyridine)palladium(II) chloride. This design utilizes CPCs at the two sides of the pincer-type ligand to improve the overall structural stability, and hence catalytic activity. It was later discovered that this palladium complex can be applied to copper-free Sonogashira coupling reaction. With different alkyl or aryl bromides and terminal alkynes, it can form carbon-carbon bond coupling product. This research demonstrates a new bis-CPC palladium complex with moderate catalytic ability and its potential for other catalytic applications.

關鍵字(中)

★ 卡本

關鍵字(英)

★ carbone

論文目次

摘要 i
ABSTRACT ii
致謝 iii
目錄 v
圖目錄 viii
式目錄 xi
表目錄 xiii
附圖目錄 xiv
簡稱說明 xviii
第一章緒論 1
1-1 前言 1
1-2 膦化物 3
1-3 碳烯 6
1-4 卡本 (carbone) 9
1-4-1 同碳雙膦烷 (carbodiphosphorane, CDP) 9
1-4-2 同碳雙碳烯 (carbodicarbene, CDC) 11
1-4-3 同碳膦烷碳烯 (carbophosphinocarbene, CPC) 16
1-5 鉗型金屬錯合物 19
1-6 鈀金屬催化偶聯 22
1-6-1 鈀金屬催化偶聯碳碳鍵合成方法 22
1-6-2 芳基鹵與末端炔之間的鈀金屬催化偶聯反應 24
1-7 研究動機 30
第二章結果與討論 31
2-1 同碳膦烷碳烯之合成及探討 31
2-1-1 雙同碳膦烷碳烯鈀金屬鉗型錯合物之合成 34
2-1-2 雙同碳膦烷碳烯鈀金屬鉗型錯合物之晶體結構 38
2-1-3 雙同碳膦烷碳烯鈀金屬鉗型錯合物光譜分析 40
2-2 薗頭偶合催化反應的最佳化條件 43
2-3 不同官能基衍生物的反應性 50
2-3-1 溴苯環衍生物的反應性 50
2-3-2 末端炔衍生物的反應性 52
第三章結論 54
第四章實驗方法 55
4-1 實驗儀器 55
4-1-1 核磁共振儀 (Nuclear magnetic resonance spectrometer) 56
4-1-2 X-ray單晶繞射解析 (X-ray diffractometer) 57
4-2 藥品與溶劑 55
4-3 合成步驟 58
4-4 薗頭偶合催化反應的步驟 64
參考文獻 77
附錄1 X-ray晶體與數據 80
附錄2 化合物光譜圖 82

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指導教授

王朝諺陳銘洲(Tiow-Gan Ong Ming-Chou Chen)

審核日期

2021-9-15

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