同碳雙碳烯之錳金屬與錸金屬錯合物的合成、鑑定及反應性探討;Synthesis, Characterization and Reactivity of Carbodicarbene Mn(I) and Re(I) Polycarbonyl Complexes

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題名:	同碳雙碳烯之錳金屬與錸金屬錯合物的合成、鑑定及反應性探討;Synthesis, Characterization and Reactivity of Carbodicarbene Mn(I) and Re(I) Polycarbonyl Complexes
作者:	陳琮倫;Chen, Chung-Lun
貢獻者:	化學學系
關鍵詞:	卡本;同碳雙碳烯;第七族過渡金屬
日期:	2024-07-11
上傳時間:	2024-10-09 15:21:35 (UTC+8)
出版者:	國立中央大學
摘要:	卡本 (carbone) 是以零價碳為中心並以兩側基團透過配位鍵來穩定的有機配體。在不同類型卡本中，同碳雙碳烯 (carbodicarbene, CDC) 有著強大的路易斯鹼兼具優秀的穩定性，且空間上擁有多元的靈活性，也因此CDC在有機金屬催化劑的設計應用上展現無限的潛力。在本論文我們使用單牙基與雙牙基的CDC配位在錸(I)與錳(I)金屬上，然而不同型態的CDC可以形成不同羰基數量的金屬錯合物M(CDC)(CO)4與M(CDC)(CO)3X (M = Re、Mn, X = Cl, Br)；其中，第七族過渡金屬會與單牙基CDC上的甲基發生碳-氫鍵活化，以共價鍵的形式鍵結到金屬上，形成M(CDC)(CO)4，然而具有四個羰基的錸金屬錯合物通常被認為是CO2還原機制中的中間體或瞬態物種，這是許多機制研究專家不斷追求的物種，也因此我們利用各種光譜方法來對此物種進行更深入研究。為了比較不同型態CDC所形成的錸金屬錯合物，我們以紅外光譜以及紫外光譜進行鑑定，並且搭配理論計算結果來作探討；另外，我們還深入研究CDC與錸金屬的合成反應機制，並成功從反應中分離出金屬與CDC以CO為架橋連接的金屬錯合物結構，透過氫譜監測判定為此反應的中間體。除此之外，為了測試它們作為電催化劑去還原CO2的潛力，我們將合成的錸(I)錯合物利用循環伏安法進行研究，發現其電催化的可行性。 ;Carbone is a zero-valent carbon as the center stabilized by coordinating groups on both sides. In the field of carbones, Carbodicarbene (CDC) exhibits great potential in the design and application of organic metal catalysts due to its strong Lewis basicity, excellent stability, and diverse flexibility. In this thesis, we used CDC coordination with monodentate and bidentate bases on rhenium (I) and manganese (I) metals. However, different types of CDC can form metal complexes M(CDC)(CO)4 and M(CDC)(CO)3Cl (M = Re、Mn, X = Cl, Br) with different numbers of carbonyl groups; Among them, the seventh group transition metal will undergo carbon hydrogen bonding activation with the methyl group on the monodentate CDC, coordinating with the metal in the form of covalent bonds to form M(CDC)(CO)4. However, rhenium metal complexes with four carbonyl groups draw special interest. For example, Re(L)(CO)4 were often considered as the intermediate or transient species in the CO2 reduction mechanism, and therefore this species is worth further investigation. In order to compare the rhenium metal complexes formed by different types of CDC, we identified them using FT-IR and UV-Vis spectra, and explored them with theoretical calculation results; In addition, we also conducted in-depth research on the synthesis reaction mechanism between CDC and rhenium metal, and successfully isolated a metal dislocation structure with CO bridging connection between the metal and CDC from the reaction. Through 1H NMR spectrum monitoring, we identified the intermediate of this reaction. In addition, to test their potential as electrocatalysts for reducing CO2, we studied the synthesized Re(I) complexes using cyclic voltammetry and found their electrocatalytic feasibility.
顯示於類別:	[化學研究所] 博碩士論文

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