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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 陳竹亭(Jwu-Ting Chen) | |
dc.contributor.author | Chia-Ching Wang | en |
dc.contributor.author | 王嘉慶 | zh_TW |
dc.date.accessioned | 2021-06-16T22:58:12Z | - |
dc.date.available | 2015-08-16 | |
dc.date.copyright | 2012-08-16 | |
dc.date.issued | 2012 | |
dc.date.submitted | 2012-08-08 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/64732 | - |
dc.description.abstract | 本篇論文中主要合成五元環之硫醚-碳烯的鈀錯合物,探討其五、六元環的金屬環在配位化學上之差異、丙烯基鈀錯合物的異構及催化。
甲基-及乙基-為連結的硫醚-咪唑鹽類已被成功的合成與鑑定。此系列硫醚-咪唑鹽類與氧化銀作用所生成硫醚-碳烯之銀錯合物可再與鈀金屬前驅物進行金屬置換反應,得到(S-NHC)PdCl2形式的硫醚-碳烯之鈀錯合物。(S-NHC)PdCl2錯合物可由甲基-連結的硫醚-碳烯構成五元環的金屬環錯合物,而此類錯合物可加入三苯基磷反應測定硫醚-碳烯配基對金屬鈀是否具有半惰性的性質。我們將五元環的金屬錯合物進行此反應,得到三苯基磷取代氯離子的陽離子產物,然而,此產物與文獻中的三苯基磷取代硫醚基之六元環產物不同。由此取代反應可得知六元環錯合物上的硫醚配位基具有半惰性的性質亦或五元環錯合物之配基具較六元環環錯合物之配基強的鉗合效應。 硫醚-氮雜環碳烯的丙烯基鈀錯合物以(S-NHC)Pd(allyl-R)X (R = 氫, 甲基, 苯基; X = 氯, 四氟硼酸, 六氟磷酸)的形式也已成功合成,並能有效的催化不飽和烯烴氫化反應。此類錯合物已用核磁共振技術及X光結晶學鑑定其結構,顯示出硫醚基與丙烯基之取代基在同方位之順式結構。從二維核磁共振技術中,發現此系列丙烯基鈀錯合物具有內與外異構物,由於氮雜環碳系具有強的反式效應,內外異構物可經由η3-η1-η3異構化或經由硫醚基的反轉彼此互相轉換。變溫核磁共振實驗中,求得η3-η1-η3異構化及硫醚基的反轉能量屏障。 | zh_TW |
dc.description.abstract | The hemilability of six- and seven- membered ring metallacycle of thioether-functionalized NHC palladium complexes were observed in solution; therefore, the five-membered ring metallacycle complexes which were constituted by the methyl- tethered thioether-NHC lgands could also exhibit hemilabile behavior in solution.
The methyl- and ethyl-tethered thioether(S)-imidazolium salts have been successfully synthesized and employed to afford the N-heterocyclic carbene (NHC) silver derivatives as carbene precursors of transmetallation. The resulting (S-NHC)PdCl2 complexes constructing with five-membered palladacycles were characterized by NMR techniques and X-ray crystallography. The coordination of thioether group could be displaced by additional PPh3 indicative of the hemilability of S-NHC ligand. Unlike the ethyl-tethered (S-NHC)PdCl2 complex, the cationic methyl-tethered S-NHC palladium complex in the formula of [(S-NHC)Pd(PPh3)Cl]Cl was also accompanied in the reaction resulted from the stronger chelating effect of five-membered palladacycles. A series of (S-NHC)Pd(allyl-R)X (R = H, Me, Ph and X = Cl, BF4, PF6) complexes has been synthesized and characterized by NMR spectroscopy and X-ray crystallography, which shows the cis configuration of the NHC and unsubstituted allylic groups in their square planar geometries. A rapid exo-endo exchange of the allylic group was observed via η3-η1-η3 isomerization in 2D NMR spectra, which was attributed to the strong trans influence of the carbene donor. The energy barriers of the η3-η1-η3 isomerization and the rapid inversion of sulfur atom were examined by variable-temperature NMR techniques. These S-NHC allylic palladium complexes were evaluated for the reaction of olefins hydrogenation showing comparable activities with literature reports. | en |
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dc.description.tableofcontents | Table of Content
Chapter 1. Introduction of N-Heterocyclic Carbene (NHC) Complexes 1 1-1. Introduction of Carbene 1 1-2. N-Heterocyclic Carbene metal complexes 5 1-3. Sulfur-Functionalized NHC Complexes 10 1-3-1. Thiolato-NHCs Complexes 12 1-3-2. Thiophene-NHCs Complexes 13 1-3-3. Thioether-NHCs Complexes 16 1-4. Goal of this Thesis 22 Chapter 2. Synthesis and Characterization of Palladium Complexes Bearing Unsymmetric Thioether-NHC Bidentate Ligands 24 2-1. Thioether-NHC Silver Complexes 24 2-1-1. Synthesis of Thioether-Imidazolium Salts 24 2-1-2. Synthesis of Thioether-NHC Silver Complexes 25 2-2. Thioether-NHC PdCl2 Complexes 26 2-2-1. Synthesis and Characterization of Zwitterionic Palladium Complex 26 2-2-2. Synthesis and Characterization of PdCl2 Complexes 29 2-2-3. Hemilability of S-NHC PdCl2 Complexes 33 2-3. X-Ray Structural Analysis 40 Chapter 3. Synthesis, Characterization and Isomerization of Palladium Allylic Complexes Bearing Unsymmetric Thioether-NHC Bidentate Ligands 44 3-1. Thioether-NHC Palladium Allylic complexes 44 3-1-1. Synthesis of Palladium Allylic Complexes 44 3-1-2. Characterization of Neutral [(S-NHC)Pd(allyl-R)]Cl Complexes 45 3-1-3. The Dynamic Behavior in Solution of Neutral [(S-NHC)Pd(allyl-R)]Cl Complexes 50 3-1-4. Characterization of Cationic Palladium Allylic Complexes 57 3-1-5. The Dynamic Behavior in Solution of Cationic Palladium Allylic Complexes 62 3-2. X-Ray Structural Analysis 69 Chapter 4. Catalytic Applications of Thioether-NHC Palladium Allylic Complexes 77 4-1. Hydrogenation Catalyzed by Thioether-NHC Palladium Allylic Complexes 77 Chapter 5. Conclusion 84 Chapter 6. Experimental Section 86 6-1. General Procedures 86 6-2. Synthesis and Spectral Characterization 87 6-3. General Procedure for Hydrogenation 121 6-4. X-ray Crystallographic Analysis 122 6-5. General Procedure for VT-NMR Isomerization Kinetics 122 References 124 Appendix 130 List of Schemes Scheme 1-1. Frontier orbitals and possible electron configurations for carbene carbon atoms 2 Scheme 1-2. Electronic configuration and resonance structures of heterocyclic five-membered carbenes containing an X2C: carbene center 5 Scheme 1-3. Synthesis of the dimer {AAI}2 by α-elimination from AA 5 Scheme 1-4. Attempted synthesis of carbene BI from imidazolium salts B 6 Scheme 1-5. Arduengo’s synthesis of the first stable N-heterocyclic carbene IAd 6 Scheme 1-6. Dimeric and mononuclear bis(thiolato)-NHC complexes 12 Scheme 1-7. Thiolato-NHCs complexes derived from (-)-levamisole. 13 Scheme 1-8. Syntheses of Ag(I) complexes of thiophene bridged bis-NHC ligands and tetrafluoroborate complexes 14 Scheme 1-9. Synthesis of thiophene bridged bis-imidazolium ligand and complexes 15 Scheme 1-10. Rotameric mixture of palladium complexes with thiophene-tethered NHC ligands 16 Scheme 1-11. Reactivity and hemilability of thioether–NHC palladium complex reported by Huynh et al. 18 Scheme 1-12. Hemilability of thioether-NHC compounds and their Pd complexes 19 Scheme 1-13. Synthetic pathway for thioether-NHC Ni, Pd and Rh complexes 20 Scheme 1-14. Synthesis of pseudo-pincer and NHC-SNHC pincer palladium Complexes 21 Scheme 2-1. Synthesis of the thioether-functionalized imidazolium salts 24 Scheme 2-2. Synthesis of the NHC silver complexes 26 Scheme 2-3. Synthesis of the methyl- and ethyl- thioether-NHC zwitterionic palladium complexes reported by Braunstein et al. and Labande et al. 26 Scheme 2-4. Equilibriums of (HL1)PdCl3 and (HL1)2PdCl4 in CH3CN 29 Scheme 2-5. Deprotonation reaction of zwitterionic palladium complexes reported by Braunstein et al. and Labande et al. 29 Scheme 2-6. Deprotonation reaction of zwitterionic complexes and synthetic pathway of (L1)PdCl2 and (L1)2PdCl2 complexes 33 Scheme 2-7. Thioether displacement reaction of six- and seven- membered ring complexes reported by Braunstein et al. and Huyn et al. 34 Scheme 2-8. Reaction of (L1)PdCl2 with one equivalent PPh3 34 Scheme 3-1. Synthetic pathways for S-NHC palladium allylic complexes 44 Scheme 3-2. Proposed η3-η1-η3 isomerization in associative type mecahnism for neutral palladium complexes 56 Scheme 3-3. Proposed pathways of isomerization for cationic palladium complexes 68 Scheme 4-1. Mercury poison experiment for the hydrogenation catalyzed by 1a” 81 Scheme 4-2. Proposed the possible mechanism of hydrogenation 83 List of Tables Table 2-1. Selected bond distances (A) and angles (◦) 43 Table 3-1. Selected 1H NMR data of neutral palladium allyl complexes 50 Table 3-2. Selected 13C NMR data of neutral palladium allyl complexes 50 Table 3-3. Kinetic data of dynamic process for 1c’ 64 Table 3-4. Selected bond distance (A) and angles (◦) 75 Table 4-1. Optimization for 1,1-diphenylethylene hydrogenation in the presence of base 78 Table 4-2. Complex scope for hydrogenation of 1,1-diphenyethylene 79 Table 4-3. Substrate scope for hydrogenation 82 List of Figure Figure 1-1. Relationship between the carbene bond angle and the nature of the frontier orbitals 1 Figure 1-2. The typical structure for Fisher, Schrock and N-Heterocyclic carbenes and their bonding orbitals toward metals 3 Figure 1-3. Perturbation orbital diagrams showing the influence of the inductive effects 4 Figure 1-4. Grubbs’ second generation catalyst and olefin metathesis 7 Figure 1-5. Correlation of the average νCO values for [(L)Ir(CO)2Cl] complexes with the Tolman electronic parameters (TEP) 9 Figure 1-6. Examples of donor-functionalized NHC ligands 10 Figure 1-7. Sulfonate-NHCs and sulfonamide-NHCs ligands 11 Figure 1-8. Aryl-tethered thioether-imidazolium salts 16 Figure 1-9. Alkyl-tethered thioether-NHC ruthenium complexes, and ferrocenyl thioether-NHC iridium and rhodium complexes. 20 Figure 1-10. Chiral cationic thioether-NHCs palladium and rhodium complexes. 22 Figure 2-1. Section of 1H NMR spectrum of (HL1)PdCl3 (400 MHz, CD3CN, 298K) 27 Figure 2-2. Section of 1H NMR and 13C NMR spectrum of cis-bis-(L1)2PdCl2 (400 MHz, CD3CN, 298K) 31 Figure 2-3. 1H NMR spectrum of (L1)PdCl2(PPh3) (400 MHz, CDCl3, 298K) 35 Figure 2-4. Section of 1H-13C-HMBC NMR spectrum (400 MHz, CDCl3, 298K) in the aromatic region for (L1)PdCl2(PPh3) 36 Figure 2-5. Section of the 1H NMR 2D NOESY spectrum (400 MHz, CDCl3, 298K) in the aromatic and Mes-CH3 region for (L1)PdCl2(PPh3) 37 Figure 2-6. Ball-and-stick model of six-membered ring metallacycle (a) and five -member ring metalacycle complexes 40 Figure 2-7. ORTEP plot of complex anti-(L1)2PdCl2 with atom labeling. Hydrogen atoms are omitted for clarity 41 Figure 2-8. ORTEP plot of complex (L1)PdCl2(PPh3) with atom labeling. Hydrogen atoms are omitted for clarity 42 Figure 3-1. 1H NMR spectrum of 1a (400 MHz, CDCl3, 298 K) 45 Figure 3-2. Possible isomers of palladium(R-allyl) complex 46 Figure 3-3. 1H NMR spectrum of 1c (400 MHz, CDCl3, 298 K) 47 Figure 3-4. Section of 1H NMR 2D NOESY (400 MHz, CDCl3, 298K) spectrum in the aromatic and Mes-CH3 region for 1c 48 Figure 3-5. 1H NMR spectrum of 1c (400 MHz, CD3CN, 298 K) 49 Figure 3-6. Selective areas of variable-temperature 1H spectra of 1c (500 MHz CD3CN) 51 Figure 3-7. η3-η1-η3 isomerization process for [PdBr(η3-C3H5)(IPr)] 52 Figure 3-8. 1H NMR 2D NOESY spectrum (500 MHz, CD3CN, 228 K) of 1c showing positive (circle) NOE and negative exchange (arrows) cross-peaks. 53 Figure 3-9. η3-η1-η3 isomerization process for [Pd(η3-2-Me-C3H4)(PTFA)]Tf reported by Manzano et al. 55 Figure 3-10. 1H NMR spectrum of 1c’ (400 MHz, CDCl3, 298 K) 57 Figure 3-11. 1H NMR spectrum of 1c’ (400 MHz, CD3CN, 298 K) 58 Figure 3-12. 1H NMR spectrum of 3a” (400 MHz, CDCl3, 298 K) 59 Figure 3-13. 1H NMR 2D NOESY spectrum (400 MHz, CD3CN, 298 K) of 1c’ showing positive (circle) NOE and negative exchange (arrows) cross-peaks 60 Figure 3-14. Section of 1H NMR 2D NOESY (400 MHz, CDCl3, 298K) spectrum for 1c’ 60 Figure 3-15. Proposed equilibria for pincer S-NHC Pd complex in solution with in-place S inversion, reported by Braunstein et al 61 Figure 3-16. Selective areas of variable-temperature 1H spectra of 1c’ (500 MHz, CD2Cl2) 62 Figure 3-17. Selective areas of variable-temperature 1H spectra of 1c’ (500 MHz, CD2Cl2) 63 Figure 3-18. Section of 1H NMR 2D NOESY (500 MHz, CD2Cl2, 196K) spectrum of 1c’ 64 Figure 3-19. Section of 1H NMR 2D NOESY (500 MHz, CD2Cl2, 196K) spectrum of 1c’ 65 Figure 3-20. Erying plot for exo-SCH3 of 1c’ from 193-298 K 67 Figure 3-21. ORTEP drawing and ball-and-stick model of neutral complex 1a, and all hydrogen atoms are omitted for clarity 69 Figure 3-22. Bottom view of endo-1a’ (a), and exo-1b’ (b); the distance between C5-C32 for endo-1a’ (c), and exo-1b’ (d) 70 Figure 3-23. ORTEP plot of complex 1a’ with atom labeling. Hydrogen atoms and counterion, BF4 are omitted for clarity 72 Figure 3-24. ORTEP plot of complex 1b’ with atom labeling. Hydrogen atoms and counterion, BF4 are omitted for clarity 72 Figure 3-25. ORTEP plot of complex 1c’ with atom labeling. Hydrogen atoms and counterion, BF4 are omitted for clarity 73 Figure 3-26. ORTEP plot of complex 2c’ with atom labeling. Hydrogen atoms and counterion, BF4 are omitted for clarity 73 Figure 3-27. ORTEP plot of complex 3a” with atom labeling. Hydrogen atoms and counterion, PF6 are omitted for clarity 74 | |
dc.language.iso | en | |
dc.title | 含硫醚-氮雜環碳烯配位基之有機鈀錯合物之合成、異構及催化 | zh_TW |
dc.title | Synthesis and Catalysis of Thioethers-Functionalized N-Heterocyclic Carbene Palladium Complexes | en |
dc.type | Thesis | |
dc.date.schoolyear | 100-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 林英智(Ying-Chih Lin),劉緒宗(Shiuh-Tzung Liu) | |
dc.subject.keyword | 氮雜環碳烯,硫醚,鈀,丙烯基,異構, | zh_TW |
dc.subject.keyword | N-Heterocyclic Carbene,Thioether,Palladium,allyl,Isomerization, | en |
dc.relation.page | 151 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2012-08-09 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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