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

、線上人數：49

、訪客IP：18.119.17.147

姓名	陳琮倫(Chung-Lun Chen) 查詢紙本館藏	畢業系所	化學學系
論文名稱	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)
檔案	[Endnote RIS 格式] [Bibtex 格式] [相關文章] [文章引用] [完整記錄] [館藏目錄] 至系統瀏覽論文 ( 永不開放)
摘要(中)	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。
摘要(英)	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.
關鍵字(中)	★ 卡本 ★ 同碳雙碳烯 ★ 第七族過渡金屬	關鍵字(英)
論文目次	摘要 I Abstract II 誌謝 III 目錄 IV 名詞簡稱 VII 圖目錄 VIII 式目錄 XI 表目錄 XIII 附表目錄 XIV 附圖目錄 XV 第一章緒論 1 1.1 前言 1 1.2 碳烯 Carbene 2 1.3 卡本 Carbone 7 1.3.1 彎曲型重烯 Bent allene 7 1.3.2 同碳雙碳烯 Carbodicarbene 8 1.4 第七族過渡金屬 10 1.4.1 第七族過渡金屬之二氧化碳還原催化劑發展 11 1.5 第七族過渡金屬之卡本錯合物 14 1.6 研究動機 16 第二章結果與討論 17 2.1 同碳雙碳烯前驅物之合成與探討 17 2.1.1 苯並咪唑前驅物之合成 19 2.1.2 苯並噻唑前驅物之合成 22 2.1.3 苯並噁唑前驅物之合成 23 2.1.4 含有苯並噻唑/噁唑的同碳雙碳烯之合成 24 2.2 同碳雙碳烯的金屬錯合物之合成與探討 26 2.2.1 錸(I)金屬錯合物之合成 26 2.2.2 錳(I)金屬錯合物之合成 28 2.3 同碳雙碳烯的金屬錯合物之晶體結構 30 2.3.1 錸金屬錯合物之晶體結構 30 2.3.2 錳金屬錯合物之晶體結構 35 2.4 同碳雙碳烯金屬錯合物之光譜鑑定 38 2.4.1 紅外光譜之鑑定與探討 38 2.4.2 紫外光譜吸收之鑑定及分子軌域的探討 43 2.4.3 循環伏安法之鑑定 47 2.5 卡本金屬錯合物反應性之研究與探討 49 2.5.1 合成卡本錸金屬錯合物之反應性研究 49 2.5.2 電化學反應性之研究 58 第三章結論 61 第四章實驗方法 62 4.1 溶劑與藥品 62 4.2 實驗儀器 62 4.2.1 核磁共振儀 (Nuclear magnetic resonance spectrometer) 62 4.2.2 紅外光譜儀 (Fourier-transform infrared spectroscopy) 63 4.2.3 X射線單晶繞射儀 (X-ray diffractometer) 63 4.2.4 高解析磁場質譜儀 (High resolution mass spectrometer) 63 4.2.5 紫外光-可見光光譜儀 (Ultraviolet-visible spectroscopy) 64 4.2.6 電化學分析儀 (Electrochemical Work Station) 64 4.3 合成步驟 65 參考文獻 83 附錄1. X-ray 晶體與數據 87 附錄2. NMR光譜圖 99 附錄3. FTIR光譜全圖 120
參考文獻	(1) Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An overview of N-heterocyclic carbenes. Nature 2014, 510, 485-496. (2) Arduengo III, A. J.; Harlow, R. L.; Kline, M. A stable crystalline carbene. J. Am. Chem. Soc. 1991, 113, 361-363. (3) Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. Metal complexes of N‐heterocyclic carbenes—a new structural principle for catalysts in homogeneous catalysis. Angew. Chem., Int. Ed. Engl. 1995, 34, 2371-2374. (4) Vougioukalakis, G. C.; Grubbs, R. H. Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts. Chem. Rev. 2010, 110, 1746-1787. (5) Chan, K.-T.; Tsai, Y.-H.; Lin, W.-S.; Wu, J.-R.; Chen, S.-J.; Liao, F.-X.; Hu, C.-H.; Lee, H. M. Palladium complexes with carbene and phosphine ligands: synthesis, structural characterization, and direct arylation reactions between aryl halides and alkynes. Organometallics 2010, 29, 463-472. (6) Lavallo, V.; Canac, Y.; Präsang, C.; Donnadieu, B.; Bertrand, G. Stable cyclic (alkyl)(amino) carbenes as rigid or flexible, bulky, electron-rich ligands for transition-metal catalysts: a quaternary carbon atom makes the difference. Angew. Chem., Int. Ed. 2005, 44, 5705-5709. (7) Klementyeva, S. V.; Abramov, P. A.; Somov, N. V.; Dudkina, Y. B.; Budnikova, Y. H.; Poddel’sky, A. I. Deprotonation of Benzoxazolium Salt: Trapping of a Radical-Cation Intermediate. Org. Lett. 2019, 21, 946-950. (8) Zhang, J.; Li, T.; Li, X.; Lv, A.; Li, X.; Wang, Z.; Wang, R.; Ma, Y.; Fang, R.; Szostak, R. Thiazol-2-ylidenes as N-Heterocyclic carbene ligands with enhanced electrophilicity for transition metal catalysis. Commun. Chem. 2022, 5, 60. (9) Soriano, E.; Fernández, I. Allenes and computational chemistry: from bonding situations to reaction mechanisms. Chem. Soc. Rev. 2014, 43, 3041-3105. (10) Saalfrank, R. W.; Maid, H. Roots: From carbenes to allenes and coordination polymers Ever present never twice the same. Chem. Commun. 2005, 5953-5967. (11) Dyker, C. A.; Lavallo, V.; Donnadieu, B.; Bertrand, G. Synthesis of an extremely bent acyclic allene (a “carbodicarbene”): a strong donor ligand. Angew. Chem., Int. Ed. 2008, 47, 3206-3209. (12) Tonner, R.; Frenking, G. C(NHC)2: Divalent Carbon(0) Compounds with N-Heterocyclic Carbene Ligands—Theoretical Evidence for a Class of Molecules with Promising Chemical Properties. Angew. Chem., Int. Ed. 2007, 46, 8695-8698. (13) Ruiz, D. A.; Melaimi, M.; Bertrand, G. Carbodicarbenes, carbon (0) derivatives, can dimerize. Chem. Asian J. 2013, 8, 2940-2942. (14) 劉書凱. 同碳膦烷碳烯-具有高度發展潛力的新型態卡本. 國立陽明交通大學, 新竹市, 博士論文, 2021. (15) Rotundo, L.; Grills, D. C.; Gobetto, R.; Priola, E.; Nervi, C.; Polyansky, D. E.; Fujita, E. Photochemical CO2 Reduction Using Rhenium (I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects. ChemPhotoChem 2021, 5, 526-537. (16) Broeck, S. M. V.; Cazin, C. S. Manganese-N-heterocyclic carbene (NHC) complexes–An overview. Polyhedron 2021, 205, 115204. (17) Hawecker, J.; Lehn, J.-M.; Ziessel, R. Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)3Cl (bipy= 2, 2′-bipyridine). J. Chem. Soc., Chem. Commun. 1984, 328-330. (18) Sullivan, B. P.; Bolinger, C. M.; Conrad, D.; Vining, W. J.; Meyer, T. J. One-and two-electron pathways in the electrocatalytic reduction of CO2 by fac-Re(bpy)(CO)3Cl (bpy= 2, 2′-bipyridine). J. Chem. Soc., Chem. Commun. 1985, 1414-1416. (19) Bourrez, M.; Molton, F.; Chardon-Noblat, S.; Deronzier, A. [Mn (bipyridyl)(CO)3Br]: an abundant metal carbonyl complex as efficient electrocatalyst for CO2 reduction. Angew. Chem., Int. Ed. 2011, 50, 9903-9906. (20) Riplinger, C.; Sampson, M. D.; Ritzmann, A. M.; Kubiak, C. P.; Carter, E. A. Mechanistic contrasts between manganese and rhenium bipyridine electrocatalysts for the reduction of carbon dioxide. J. Am. Chem. Soc. 2014, 136, 16285-16298. (21) Agarwal, J.; Shaw, T. W.; Stanton III, C. J.; Majetich, G. F.; Bocarsly, A. B.; Schaefer III, H. F. NHC‐Containing Manganese (I) Electrocatalysts for the Two‐Electron Reduction of CO2. Angew. Chem., Int. Ed. 2014, 53, 5152-5155. (22) Fernández, S.; Franco, F.; Martínez Belmonte, M.; Friães, S.; Royo, B.; Luis, J. M.; Lloret-Fillol, J. Decoding the CO2 reduction mechanism of a highly active organometallic manganese electrocatalyst: direct observation of a hydride intermediate and its implications. ACS Catal. 2023, 13, 10375-10385. (23) Romão, C. C.; Kühn, F. E.; Herrmann, W. A. Rhenium (VII) oxo and imido complexes: synthesis, structures, and applications. Chem. Rev. 1997, 97, 3197-3246. (24) Sundermeyer, J.; Weber, K.; Peters, K.; von Schnering, H. G. Modeling surface reactivity of metal oxides: synthesis and structure of an ionic organorhenyl perrhenate formed by ligand-induced dissociation of covalent Re2O7. Organometallics 1994, 13, 2560-2562. (25) Klein, M.; Xie, X.; Burghaus, O.; Sundermeyer, J. r. Synthesis and characterization of a N, C, N-carbodiphosphorane pincer ligand and its complexes. Organometallics 2019, 38, 3768-3777. (26) Maser, L., M. Vogt, and R. Langer, Facial vs. Meridional Coordination Modes in ReI Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand. Z. Anorg. Allg. Chem. 2021, 647, 1518-1523. (27) Chen, W. C.; Shen, J. S.; Jurca, T.; Peng, C. J.; Lin, Y. H.; Wang, Y. P.; Shih, W. C.; Yap, G. P.; Ong, T. G. Expanding the ligand framework diversity of carbodicarbenes and direct detection of boron activation in the methylation of amines with CO2. Angew. Chem., Int. Ed. 2015, 54, 15207-15212. (28) Fürstner, A.; Alcarazo, M.; Goddard, R.; Lehmann, C. W. Coordination chemistry of ene-1, 1-diamines and a prototype" Carbodicarbene". Angew. Chem., Int. Ed. 2008, 47, 3210-3214. (29) Stanton III, C. J.; Machan, C. W.; Vandezande, J. E.; Jin, T.; Majetich, G. F.; Schaefer III, H. F.; Kubiak, C. P.; Li, G.; Agarwal, J. Re(I) NHC complexes for electrocatalytic conversion of CO2. Inorg. Chem. 2016, 55, 3136-3144. (30) Grice, K. A.; Gu, N. X.; Sampson, M. D.; Kubiak, C. P. Carbon monoxide release catalysed by electron transfer: electrochemical and spectroscopic investigations of [Re(bpy-R)(CO)4](OTf) complexes relevant to CO2 reduction. Dalton. Trans. 2013, 42, 8498-8503.
指導教授	陳銘洲王朝諺(Ming-Chou Chen Tiow-Gan Ong)	審核日期	2024-7-11
推文	facebook plurk twitter funp google live udn HD myshare reddit netvibes friend youpush delicious baidu
網路書籤	Google bookmarks del.icio.us hemidemi myshare

博碩士論文 111223015 詳細資訊