鉗型同碳雙碳烯鈀錯合物之修飾及其物理 性質與化學反應性之研究

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姓名	戴君如(Jyun-Ru Dai) 查詢紙本館藏	畢業系所	化學學系
論文名稱	鉗型同碳雙碳烯鈀錯合物之修飾及其物理性質與化學反應性之研究 (Modifications on the Pincer-Type Carbodicarbene Palladium Complex and Investigation of Their Physical Property and Chemical Reactivity)
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摘要(中)	近年由於光催化以及傳統催化機制的發展與深入，使光協同催化反應成為一熱門的研究主題。光協同催化反應通常由光敏劑以及催化劑組合而成，藉由光能代替傳統使用之熱能來驅動反應，其優點是減少高溫帶來之副反應，以及增加設計新反應之可能性。本實驗室在 2015 與 2018 年發表一種鉗型同碳雙碳烯鈀錯合物，發現它能夠催化單電子的光氧化還原及雙電子的偶聯反應。使用此化合物於光誘導碳氫活化反應，可以在不添加光敏劑的條件下進行，惟目前極少數的例子。此雙功能的催化劑在這個研究的領域上為一個很重大的進展。本論文以鉗型同碳雙碳烯鈀錯合物為研究的方向，對於此化合物進行官能基的修飾，其中設計了具有電子效應及立體效應的兩種配位基，在電子效應的部分，將具有推電子的甲氧基接在配位基上，使中心碳的孤對電子的供電子能力增加，對於光氧化還原反應有正向的影響，在立體效應的部分，將具有立體障礙的甲基接在配位基的吡啶上，使反應位點的立體障礙增大，對於催化反應造成負面的影響，透過這些研究所得到的資訊可以更深入的瞭解其反應機制並且發展更多此系統的應用。
摘要(英)	Recently, based on the accumulated understanding of photo-catalysis and conventional catalysis cycle, the combinatory synergistic catalysis become a topic of great interest. The cooperative photo-redox catalysis usually consists of a photo-sensitizer and an operating catalyst, in which photo energy is used to replace the thermal energy as the driving force. The advantages are reducing the side reactions caused by high temperature as well as increasing the possibility of designing a new state-of-art reaction. In 2015 and 2018, our lab has published the pincer-type carbodicarbene palladium complex, which is capable of catalyzing the photo-redox reaction (1e- process) and the cross-coupling (2e- process). This complex can also be utilized as both the photo-sensitizer and cross-coupling catalyst. This bifunctional catalyst is very rare and represents a significant advancement in this field of research. In this thesis, the research topic is to modify the pincer-type carbodicarbene palladium complex by designing two types of ligand for electronic effect and steric effect. To examine the electronic effect, the methoxy groups were installed on the ligand backbone to increase the sigma-donating ability. In the part of steric effect, the methyl group were installed on the ortho-position of the pyridine side-arms, blocking the trajectory of incoming substrate towards the metal center. With the information provided, we can understand mechanisms in details and develop more applications of this system.
關鍵字(中)	★ 同碳雙碳烯	關鍵字(英)	★ carbodicarbene
論文目次	摘要 i ABSTRACT i 致謝 ii 目錄 iii 圖目錄 vi 式目錄 ix 表目錄 xi 附圖目錄 xii 簡稱說明 xv 第一章緒論 1 1-1 前言 1 1-2 碳烯 2 1-3 彎曲型重烯-同碳雙碳烯 (carbodicarbene, CDC) 5 1-4 鉗型金屬錯合物 11 1-5 光氧化還原反應 15 1-6 協同光氧化還原及鈀金屬催化 19 1-7 研究動機 22 第二章結果與討論 23 2-1鉗型同碳雙碳烯前驅物之合成及探討 24 2-2鉗型同碳雙碳烯前驅物之合成 26 2-3鉗型同碳雙碳烯鈀錯合物之合成 31 2-4鉗型同碳雙碳烯鈀錯合物之結構鑑定 33 2-5鉗型同碳雙碳烯鈀錯合物之DFT計算 39 2-6鉗型同碳雙碳烯鈀錯合物之光譜鑑定 43 2-7鉗型同碳雙碳烯鈀錯合物之循環伏安法圖譜鑑定 45 2-8-1鉗型同碳雙碳烯鈀錯合物之光氧化還原催化反應 49 2-8-2鉗型同碳雙碳烯鈀錯合物之溝呂木-赫克反應 51 2-8-3鉗型同碳雙碳烯鈀錯合物之鈀金屬碳氫活化催化反應 52 第三章結論 53 第四章實驗方法 54 4-1藥品與溶劑 54 4-2-1核磁共振儀 (Nuclear magnetic resonance spectrometer) 55 4-2-2 X-ray單晶繞射解析 (X-ray diffractometer) 56 4-2-3高解析度磁場質譜儀 (High resolution magnetic sector mass spectrometer ) 56 4-2-4紫外光-可見光分光光譜儀 (Ultraviolet-visible spectroscopy) 57 4-2-5循環伏安儀(Cyclic voltammetry) 57 4-3合成步驟 58 4-4-1 C-N鍵形成的光氧化還原催化反應的步驟 73 4-4-2溝呂木－赫克交叉偶聯催化反應的步驟 76 4-4-3鈀金屬碳氫活化催化反應的步驟 77 參考文獻 78 附錄1 X-ray晶體與數據 84 附錄2化合物光譜圖 89
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指導教授	陳銘洲王朝諺(Ming-Chou Chen Tiow-Gan Ong)	審核日期	2022-8-31
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