具氧化還原性的同碳雙碳烯金錯合物和雙芽手性卡本衍生物及其金屬錯合物之合成與結構鑑定;Synthesis and Characterization of the Redox-active Carbodicarbene Gold Complexes and Bidentate BINAP-based Chiral Carbone-derivative with their Metal Complexes

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題名:	具氧化還原性的同碳雙碳烯金錯合物和雙芽手性卡本衍生物及其金屬錯合物之合成與結構鑑定;Synthesis and Characterization of the Redox-active Carbodicarbene Gold Complexes and Bidentate BINAP-based Chiral Carbone-derivative with their Metal Complexes
作者:	蔡尚廷;Tsai, Shang-Ting
貢獻者:	化學學系
關鍵詞:	卡本;手性;同碳雙碳烯;雙芽;氧化還原;錯合物;carbone;chiral;carbodicarbene;bidentate;redox-active;complex
日期:	2019-07-02
上傳時間:	2019-09-03 14:26:02 (UTC+8)
出版者:	國立中央大學
摘要:	配位基在有機金屬催化反應中扮演著重要的角色，其電子效應與立體效應影響著金屬錯合物的反應性。本實驗室主要發展的新穎配位基，是以重烯為基礎架構的衍生物－卡本，因中心碳上具有兩對未鍵結電子而擁有良好的親核能力，其取代基的設計與金屬錯合物的應用上仍有許多可發展的空間。　　本論文使用實驗室已開發的卡本－同碳雙碳烯，與AuCl-SMe2進行反應，可得到同碳雙碳烯與金配位的結構，將其進一步與雙三氟甲磺酸亞胺銀鹽 (AgNTf2) 進行反應，發現溶液由黃色迅速轉為深藍色，由X-ray單晶繞射解析得知其為兩個同碳雙碳烯與金配位，且為帶三價正電陽離子的錯合物，並具有EPR訊號，初步推測可能為配位基上帶有自由基陽離子的結構。　　另一方面在配位基的設計上，為了加入反應的鏡像選擇性，使用具大立體障礙及手性的BINAP，並以簡單的SN2反應進行合成，成功開發出具手性的雙芽卡本－同碳磷烷碳烯。為了瞭解此卡本衍生物與金屬錯合物的配位情形，及其中心碳與金屬的親核能力，我們將它與不同的金屬錯合物反應。藉由X-ray單晶繞射解析得知，其同時以三級膦取代基及中心碳與鈀金屬配位，卻僅以三級膦取代基與金配位；而在與銅錯合物的反應中，可以單配位及雙配位的方式與銅金屬鍵結，結果取決於陰離子的電子給予能力強弱。 ;Ligand design is an important part of organometallic chemistry and catalysis. The electronic parameters and steric hindrance of the ligand influence the reactivity of the metal complexes. The carbodicarbene (CDC), also known as ‘‘bent allene’’, is a new class of low-valent carbon specy. Its electron-donating ability is very strong due to its possession of two free electron pairs, which even surpasses the carbenes. It has emerged as a potential effective ligand next to the carbenes and phosphines. 　　In the first project, we have successfully isolated CDC-supported tricationic Au-complexes. The complexes are fully characterized by NMR and X-ray diffraction. These Au complexes are EPR-active that CDC moiety are shown to carried radical cations 　　In second project, we have successfully developed the chiral bidentate carbophosphinocarbene, which is based on the large steric hindrance chiral ligand ‘‘BINAP’’. In this work, we have an interesting in the electron-donating ability of the carbon center at the carbone-derivative, so we have done the experiment with palladium(II), gold(I), and copper(I) metal complexes. The single crystal X-ray structural analysis and NMR spectroscopic studies have been used to understand the coordination sphere. This carbone-derivative can play a bidentate ligand in palladium(II) complexes, but just be a monodentate ligand in gold(I) complexes. Interestingly, it can be not only monodentate ligand but also bidentate ligand in copper(I) complexes, which is dependent on the coordination ability of the counter-anion.
顯示於類別:	[化學研究所] 博碩士論文

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