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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 王朝諺 | zh_TW |
| dc.contributor.advisor | Tiow-Gan Ong | en |
| dc.contributor.author | 王語柔 | zh_TW |
| dc.contributor.author | Yu-Jou Wang | en |
| dc.date.accessioned | 2024-09-18T16:25:25Z | - |
| dc.date.available | 2024-09-19 | - |
| dc.date.copyright | 2024-09-18 | - |
| dc.date.issued | 2024 | - |
| dc.date.submitted | 2024-08-06 | - |
| dc.identifier.citation | 1. Dumas, J.-B.; Péligot, E. Mémoire sur l’esprit de bois et sur les divers composes éthérés qui en proviennent. Annal. Chim. Phys. 1835, 58,5.
2. Igau, A.; Grutzmacher, H.; Baceiredo, A.; Bertrand, G. Analogous α, α'-bis-carbenoid, triply bonded species: synthesis of a stable λ3-phosphino carbene-λ5-phosphaacetylene. J. Am. Chem. Soc. 1988, 110 (19), 6463-6466. 3. (a) Hahn, F. E.; Jahnke, M. C. Heterocyclic Carbenes: Synthesis and Coordination Chemistry. Angew. Chem., Int. Ed. 2008, 47 (17), 3122-3172. (b) de Frémont, P.; Marion, N.; Nolan, S. P. Carbenes: Synthesis, properties, and organometallic chemistry. Coord. Chem Rev. 2009, 253 (7), 862-892. 4. (a) Dröge, T.; Glorius, F. The Measure of All Rings—N‐Heterocyclic Carbenes. Angew. Chem., Int. Ed. 2010, 49 (39), 6940-6952. (b) Nelson, D. J.; Nolan, S. P. Quantifying and understanding the electronic properties of N-heterocyclic carbenes. Chem. Soc. Rev. 2013, 42 (16), 6723. (c) Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An overview of N-heterocyclic carbenes. Nature 2014, 510 (7506), 485-496. (d) Nesterov, V.; Reiter, D.; Bag, P.; Frisch, P.; Holzner, R.; Porzelt, A.; Inoue, S. NHCs in Main Group Chemistry. Chem. Rev. 2018, 118 (19), 9678-9842. 5. 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 (35), 5705-5709. 6. Moerdyk, J. P.; Schilter, D.; Bielawski, C. W. N,N’-Diamidocarbenes: Isolable Divalent Carbons with Bona Fide Carbene Reactivity. Acc. Chem. Res. 2016, 49 (8), 1458-1468. 7. Hu, C.; Wang, X.-F.; Li, J.; Chang, X.-Y.; Liu, L. L. A stable rhodium-coordinated carbene with a σ0π2 electronic configuration. Science 2024, 383 (6678), 81-85. 8. Arduengo, A. J., III; Harlow, R. L.; Kline, M. A stable crystalline carbene. J. Am. Chem. Soc. 1991, 113 (1), 361-363. 9. (a) Tonner, R.; Frenking, G. Divalent Carbon(0) Chemistry, Part 1: Parent Compounds. Chem. – Eur. J. 2008, 14 (11), 3260-3272. (b) Liu, S. K.; Shih, W. C.; Chen, W. C.; Ong, T. G. Carbodicarbenes and their Captodative Behavior in Catalysis. ChemCatChem 2018, 10 (7), 1483-1498. 10. Ramirez, F.; Desai, N. B.; Hansen, B.; McKelvie, N. HEXAPHENYLCARBODIPHOSPHORANE, (C6H5)3PCP(C6H5)3. J. Am. Chem. Soc. 1961, 83 (16), 3539-3540. 11. (a) Kaska,W. C., Mitchell, D. K., Reichelderfer, R. F. Transition metal complexes of hexaphenylcarbodiphosphorane. J. Organomet. Chem. 1973, 47, 391–402. (b) Schmidbaur, H. Carbodiphosphorane. Nachr. Chem.Tech. Lab. 1979, 27, 620–622. 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 (45), 8695-8698. 13. (a) Chen, W.-C.; Hsu, Y.-C.; Lee, C.-Y.; Yap, G. P. A.; Ong, T.-G. Synthetic Modification of Acyclic Bent Allenes (Carbodicarbenes) and Further Studies on Their Structural Implications and Reactivities. Organometallics 2013, 32 (8), 2435-2442. (b) Hsu, Y. C.; Shen, J. S.; Lin, B. C.; Chen, W. C.; Chan, Y. T.; Ching, W. M.; Yap, G. P. A.; Hsu, C. P.; Ong, T. G. Synthesis and Isolation of an Acyclic Tridentate Bis(pyridine)carbodicarbene and Studies on Its Structural Implications and Reactivities. Angew. Chem., Int. Ed. 2015, 54 (8), 2420-2424. (c) Chen, W.-C.; Shih, W.-C.; Jurca, T.; Zhao, L.; Andrada, D. M.; Peng, C.-J.; Chang, C.-C.; Liu, S.-k.; Wang, Y.-P.; Wen, Y.-S.; et al. Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules. J. Am. Chem. Soc. 2017, 139 (36), 12830-12836. (d) Liu, S. K.; Shih, W. C.; Chen, W. C.; Ong, T. G. Carbodicarbenes and their Captodative Behavior in Catalysis. ChemCatChem 2018, 10 (7), 1483-1498. (e) Au‐Yeung, K. C.; Xiao, D.; Shih, W. C.; Yang, H. W.; Wen, Y. S.; Yap, G. P. A.; Chen, W. C.; Zhao, L.; Ong, T. G. Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner. Chem. Eur. J. 2020, 26 (72), 17350-17355. 14. (a) Walley, J. E.; Breiner, G.; Wang, G.; Dickie, D. A.; Molino, A.; Dutton, J. L.; Wilson, D. J. D.; Gilliard, J. R. J. s-Block carbodicarbene chemistry: C(sp3)‒H activation and cyclization mediated by a beryllium center. Chem. Commun. 2019, 55 (13), 1967-1970 (b) Walley, J. E.; Warring, L. S.; Wang, G.; Dickie, D. A.; Pan, S.; Frenking, G.; Gilliard, R. J. Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry. Angew. Chem., Int. Ed. 2021, 60 (12), 6682-6690. 15. (a) Dobrovetsky, R.; Stephan, D. W. Catalytic Reduction of CO<sub>2</sub> to CO by Using Zinc(II) and In Situ Generated Carbodiphosphoranes. Angew. Chem., Int. Ed. 2013, 52 (9), 2516-2519. (b) Pranckevicius, C.; Fan, L.; Stephan, D. W. Cyclic Bent Allene Hydrido-Carbonyl Complexes of Ruthenium: Highly Active Catalysts for Hydrogenation of Olefins. J. Am. Chem. Soc. 2015, 137 (16), 5582-5589. (c) Pranckevicius, C.; Liu, L. L.; Bertrand, G.; Stephan, D. W. Synthesis of a Carbodicyclopropenylidene: A Carbodicarbene based Solely on Carbon. Angew. Chem., Int. Ed. 2016, 55 (18), 5536-5540. 16. (a) Goldfogel, M. J.; Roberts, C. C.; Meek, S. J. Intermolecular Hydroamination of 1,3-Dienes Catalyzed by Bis(phosphine)carbodicarbene–Rhodium Complexes. J. Am. Chem. Soc. 2014, 136 (17), 6227-6230. (b) Roberts, C. C.; Matías, D. M.; Goldfogel, M. J.; Meek, S. J. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes. J. Am. Chem. Soc. 2015, 137 (20), 6488-6491. (c) Marcum, J. S.; Roberts, C. C.; Manan, R. S.; Cervarich, T. N.; Meek, S. J. Chiral Pincer Carbodicarbene Ligands for Enantioselective Rhodium-Catalyzed Hydroarylation of Terminal and Internal 1,3-Dienes with Indoles. J. Am. Chem. Soc. 2017, 139 (44), 15580-15583. 17. (a) Scharf, L. T.; Andrada, D. M.; Frenking, G.; Gessner, V. H. The Bonding Situation in Metalated Ylides. Chem. Eur. J. 2017, 23 (18), 4422-4434. (b) Scharf, L. T.; Gessner, V. H. Metalated Ylides: A New Class of Strong Donor Ligands with Unique Electronic Properties. Inorg. Chem. 2017, 56 (15), 8599-8607. (c) Krischer, F.; Gessner, V. H. Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents. JACS Au 2024, 4 (5), 1709-1722. 18. Tonner, R.; Frenking, G. Divalent Carbon(0) Chemistry, Part 1: Parent Compounds. Chem. Eur. J. 2008, 14 (11), 3260-3272. 19. (a) Schrock, R. R. Recent Advances in High Oxidation State Mo and W Imido Alkylidene Chemistry. Chem. Rev. 2009, 109 (8), 3211-3226. (b) Feliciano, A.; Vázquez, J. L.; Benítez‐Puebla, L. J.; Velazco‐Cabral, I.; Cruz Cruz, D.; Delgado, F.; Vázquez, M. A. Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions. Chem. Eur. J. 2021, 27 (32), 8233-8251. 20. 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 (17), 3206-3209. 21. Hsu, Y. C.; Wang, V. C. C.; Au‐Yeung, K. C.; Tsai, C. Y.; Chang, C. C.; Lin, B. C.; Chan, Y. T.; Hsu, C. P.; Yap, G. P. A.; Jurca, T.; et al. One‐Pot Tandem Photoredox and Cross‐Coupling Catalysis with a Single Palladium Carbodicarbene Complex. Angew. Chem., Int. Ed. 2018, 57 (17), 4622-4626. 22. Chen, W.-C.; Lee, C.-Y.; Lin, B.-C.; Hsu, Y.-C.; Shen, J.-S.; Hsu, C.-P.; Yap, G. P. A.; Ong, T.-G. The Elusive Three-Coordinate Dicationic Hydrido Boron Complex. J. Am. Chem. Soc. 2014, 136 (3), 914-917. 23. (a) Hollister, K. K.; Molino, A.; Breiner, G.; Walley, J. E.; Wentz, K. E.; Conley, A. M.; Dickie, D. A.; Wilson, D. J. D.; Gilliard, R. J., Jr. Air-Stable Thermoluminescent Carbodicarbene-Borafluorenium Ions. J. Am. Chem. Soc. 2022, 144 (1), 590-598. (b) Warring, L. S.; Walley, J. E.; Dickie, D. A.; Tiznado, W.; Pan, S.; Gilliard, R. J., Jr. Lewis Superacidic Heavy Pnictaalkene Cations: Comparative Assessment of Carbodicarbene-Stibenium and Carbodicarbene-Bismuthenium Ions. Inorg. Chem. 2022, 61 (46), 18640-18652. 24. Su, W.-F. Radical Chain Polymerization. Springer Berlin Heidelberg, 2013; pp 137-183. 25. (a) Rieth, A. J.; Gonzalez, M. I.; Kudisch, B.; Nava, M.; Nocera, D. G. How Radical Are “Radical” Photocatalysts? A Closed-Shell Meisenheimer Complex Is Identified as a Super-Reducing Photoreagent. J. Am. Chem. Soc. 2021, 143 (35), 14352-14359. (b) Chen, Y.; Xu, S.; Fang Wen, C.; Zhang, H.; Zhang, T.; Lv, F.; Yue, Y.; Bian, Z. Unravelling the Role of Free Radicals in Photocatalysis. Chem. Eur. J. 2024, 30 (29) 26. Gomberg, M. AN INSTANCE OF TRIVALENT CARBON: TRIPHENYLMETHYL. J. Am. Chem. Soc. 1900, 22 (11), 757-771. 27. (a) Büttner, T.; Geier, J.; Frison, G.; Harmer, J.; Calle, C.; Schweiger, A.; Schönberg, H.; Grützmacher, H. A Stable Aminyl Radical Metal Complex. Science 2005, 307 (5707), 235-238. (b) Kaim, W. Odd Electron on Nitrogen: A Metal-Stabilized Aminyl Radical. Science 2005, 307 (5707), 216-217. 28. (a) Wang, Y.; DuBois, J. L.; Hedman, B.; Hodgson, K. O.; Stack, T. D. P. Catalytic Galactose Oxidase Models: Biomimetic Cu(II)-Phenoxyl-Radical Reactivity. Science 1998, 279 (5350), 537-540. (b) Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Architecture of the Photosynthetic Oxygen-Evolving Center. Science 2004, 303 (5665), 1831-1838. 29. Krusic, P. J.; Klabunde, U.; Casey, C. P.; Block, T. F. An electron spin resonance study of the radical anions derived from metal carbene complexes of chromium, molybdenum, and tungsten. J. Am. Chem. Soc. 1976, 98 (7), 2015-2018. 30. Ganguly, S.; Ghosh, A. Seven Clues to Ligand Noninnocence: The Metallocorrole Paradigm. Acc. Chem. Res. 2019, 52 (7), 2003-2014. 31. (a) Dzik, W. I.; Zhang, X. P.; de Bruin, B. Redox Noninnocence of Carbene Ligands: Carbene Radicals in (Catalytic) C−C Bond Formation. Inorg. Chem. 2011, 50 (20), 9896-9903. (b) Ikeno, T.; Iwakura, I.; Yamada, T. Cobalt−Carbene Complex with Single-Bond Character: Intermediate for the Cobalt Complex-Catalyzed Cyclopropanation. J. Am. Chem. Soc. 2002, 124 (51), 15152-15153. 32. (a) Chan, S. C.; Gupta, P.; Engelmann, X.; Ang, Z. Z.; Ganguly, R.; Bill, E.; Ray, K.; Ye, S.; England, J. Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes. Angew. Chem., Int. Ed. 2018, 57 (48), 15717-15722. (b) Chan, S.-C.; Ang, Z. Z.; Gupta, P.; Ganguly, R.; Li, Y.; Ye, S.; England, J. Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Chromium and Cobalt Complexes. Inorg. Chem. 2020, 59 (6), 4118-4128. 33. (a) Gallego, D.; Baquero, E. A. Recent Advances on Mechanistic Studies on C‒H Activation Catalyzed by Base Metals. Open Chemistry 2018, 16 (1), 1001-1058. (b) Altus, K. M.; Love, J. A. The continuum of carbon–hydrogen (C‒H) activation mechanisms and terminology. Commun. Chem. 2021, 4(1). 34. (a) Zheng, B.; Tang, F.; Luo, J.; Schultz, J. W.; Rath, N. P.; Mirica, L. M. Organometallic Nickel(III) Complexes Relevant to Cross-Coupling and Carbon–Heteroatom Bond Formation Reactions. J. Am. Chem. Soc. 2014, 136 (17), 6499-6504. (b) Camasso, N. M.; Sanford, M. S. Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes. Science 2015, 347 (6227), 1218-1220. (c) Lin, C.-Y.; Power, P. P. Complexes of Ni(I): a “rare” oxidation state of growing importance. Chem. Soc. Rev. 2017, 46 (17), 5347-5399. 35. Krämer, T.; Gyton, M. R.; Bustos, I.; Sinclair, M. J. G.; Tan, S.-y.; Wedge, C. J.; Macgregor, S. A.; Chaplin, A. B. Stability and C–H Bond Activation Reactions of Palladium(I) and Platinum(I) Metalloradicals: Carbon-to-Metal H-Atom Transfer and an Organometallic Radical Rebound Mechanism. J. Am. Chem. Soc. 2023, 145 (25), 14087-14100. 36. Chen, W. C.; Shen, J. S.; Jurca, T.; Peng, C. J.; Lin, Y. H.; Wang, Y. P.; Shih, W. C.; Yap, G. P. A.; 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 (50), 15207-15212. 37. Alvarez, S. A cartography of the van der Waals territories. Dalton Trans., 2013, 42 (24), 8617. 38. Harry, N. A.; Saranya, S.; Ujwaldev, S. M.; Anilkumar, G. Recent advances and prospects in nickel-catalyzed C‒H activation. Catal. Sci. Technol., 2019, 9 (8), 1726-1743. 39. Oertel, A. M.; Freudenreich, J.; Gein, J.; Ritleng, V.; Veiros, L. F.; Chetcuti, M. J. Intramolecular Nitrile C–H Bond Activation in Nickel NHC Complexes: A Route to New Nickelacycles. Organometallics 2011, 30 (12), 3400-3411. 40. Wang, T.-H.; Ambre, R.; Wang, Q.; Lee, W.-C.; Wang, P.-C.; Liu, Y.; Zhao, L.; Ong, T.-G. Nickel-Catalyzed Heteroarenes Cross Coupling via Tandem C–H/C–O Activation. ACS Catal., 2018, 8 (12), 11368-11376. 41. Gómez-Gallego, M.; Sierra, M. A. Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms. Chem. Rev. 2011, 111 (8), 4857-4963. 42. Li, G.; Zheng, J.; Fang, X.; Xu, K.; Yang, Y.-F.; Wu, J.; Cao, L.; Li, J.; She, Y. N-Heterocyclic Carbene-Based Tetradentate Pd(II) Complexes for Deep-Blue Phosphorescent Materials. Organometallics 2021, 40 (4), 472-481. 43. Dible, B. R.; Sigman, M. S. Unusual Reactivity of Molecular Oxygen with π-Allylnickel(N-heterocyclic carbene) Chloride Complexes. J. Am. Chem. Soc. 2003, 125 (4), 872-873. 44. Yano, J.; Yachandra, V. K. X-ray absorption spectroscopy. Photosynth. Res. 2009, 102 (2-3), 241-254. 45. Colpas, G. J.; Maroney, M. J.; Bagyinka, C.; Kumar, M.; Willis, W. S.; Suib, S. L.; Mascharak, P. K.; Baidya, N. X-ray spectroscopic studies of nickel complexes, with application to the structure of nickel sites in hydrogenases. Inorg. Chem. 1991, 30 (5), 920-928. 46. Westawker, L. P.; Khusnutdinova, J. K.; Wallick, R. F.; Mirica, L. M. Palladium K-edge X-ray Absorption Spectroscopy Studies on Controlled Ligand Systems. Inorg. Chem. 2023, 62 (51), 21128-21137. 47. (a) Jacobs, S. A.; Margerum, D. W. Solution properties of bis(dipeptide)nickelate(III) complexes and kinetics of their decomposition in acid. Inorg. Chem. 1984, 23 (9), 1195-1201. (b) Adhikari, D.; Mossin, S.; Basuli, F.; Huffman, J. C.; Szilagyi, R. K.; Meyer, K.; Mindiola, D. J. Structural, Spectroscopic, and Theoretical Elucidation of a Redox-Active Pincer-Type Ancillary Applied in Catalysis. J. Am. Chem. Soc. 2008, 130 (11), 3676-3682. 48. Shimazaki, Y.; Tani, F.; Fukui, K.; Naruta, Y.; Yamauchi, O. One-Electron Oxidized Nickel(II)−(Disalicylidene)diamine Complex: Temperature-Dependent Tautomerism between Ni(III)−Phenolate and Ni(II)−Phenoxyl Radical States. J. Am. Chem. Soc. 2003, 125 (35), 10512-10513. 49. Khusnutdinova, J. R.; Rath, N. P.; Mirica, L. M. The Aerobic Oxidation of a Pd(II) Dimethyl Complex Leads to Selective Ethane Elimination from a Pd(III) Intermediate. J. Am. Chem. Soc. 2012, 134 (4), 2414-2422. 50. Allen, D. W.; Dommett, S. J. R. A comparison of the donor properties of some heterocyclic and ortho-substituted acyclic triarylphosphines towards nickel(II) bromide. The importance of steric effects. Inorganica Chimica Acta 1978, 31, L369-L370. 51. Standley, E. A.; Smith, S. J.; Müller, P.; Jamison, T. F. A Broadly Applicable Strategy for Entry into Homogeneous Nickel(0) Catalysts from Air-Stable Nickel(II) Complexes. Organometallics 2014, 33 (8), 2012-2018. 52. Jafarpour, L.; Stevens, E. D.; Nolan, S. P. A sterically demanding nucleophilic carbene: 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Thermochemistry and catalytic application in olefin metathesis. J. Org. Chem., 2000, 606 (1), 49-54. | - |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/95861 | - |
| dc.description.abstract | 同碳雙碳烯（Carbodicarbene）是一種獨特的碳零價結構，其中心碳原子上具有兩對孤電子對，並由兩個中性電子給予配位基L穩定。在有機金屬和催化領域中，以具有良好的σ給予電子能力的配位基而聞名，與金屬搭配合成錯合物做後續更多元的應用，屬於發展日漸活躍的研究領域。
本論文以同碳雙碳烯作為配位基，合成一系列鎳二價金屬錯合物，此結構是透過同碳雙碳烯中，其中一個甲基側臂進行碳-氫活化形成的。在合成過程中，我們發現部分鎳二價前驅物被還原，隨後形成同碳雙碳烯配位的鎳一價錯合物。因此，我們以研究鎳二價錯合物的形成機制為目標，並根據上述觀察結果提出兩種機制：鹼基輔助碳-氫活化和自由基反彈碳-氫活化。 此外，我們也合成了以同碳雙碳烯和碳烯作為配位基的鎳二價和鈀二價金屬錯合物，用於研究同碳雙碳烯與不同金屬配位後的氧化還原活性。透過單電子氧化反應，我們成功合成並分離出兩種錯合物的氧化物質。藉由X光單晶繞射儀解析其晶體結構，以X光吸收光譜確認中心金屬價數，並以電子順磁共振光譜儀輔佐分析電子結構。結果表明，鎳二價錯合物的氧化主要發生在金屬中心，而鈀二價錯合物的氧化主要發生在同碳雙碳烯的配位基中心。 | zh_TW |
| dc.description.abstract | Carbodicarbenes, a divalent carbon(0) species supported by two neutral donor groups (L), possess two lone pairs of electrons on their central carbon atom. Due to their strong σ donating ability, they have been reliable ligands in organometallic and catalysis.
In this work, a series of novel CDC‒nickel(II) complexes were synthesized. They were generated via intramolecular C(sp3)‒H bond activation at one of the CDC methyl side arms. During the synthesis, we found that the nickel(II) precursor was partially reduced, and later formed the CDC‒nickel(I) complex. Accordingly, we sought to investigate the mechanism of formation of CDC‒nickel(II) complexes, and two mechanisms were proposed: base-assisted and radical-rebound C‒H activation. In addition, we have also synthesized nickel(II) and palladium(II) complexes bearing CDC and NHC as ligands. They were used for probing the redox activity of CDC in coordination with different metals. Upon single-electron oxidation, we successfully obtained the oxidized species of both complexes. Their electronic structures were investigated by a combination of EPR, X-ray absorption spectroscopies, and X-ray crystallography. The results indicated that oxidation of the nickel(II) complex occurs mostly on the metal center, whereas that of the palladium(II) complex is CDC ligand-centered. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2024-09-18T16:25:25Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2024-09-18T16:25:25Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 摘要 i
ABSTRACT ii Acknowledgments iii Table of Contents iv Abbreviations xvi List of Tables xiv List of Figures viii List of Schemes xv CHAPTER 1 Introduction 1 1-1 Carbenes 1 1-1-1 Introduction 1 1-1-2 N-Heterocyclic Carbene (NHC) 3 1-2 Carbones 4 Properties of carbone 5 1-3 Inherently variant coordination behavior of carbenes and carbones 7 1-3-1 Carbenes in coordination complexes 8 1-3-2 Carbones in coordination complexes 9 1-4 Metal-assisted persistent organic radicals 13 CHAPTER 2 Motivation 17 CHAPTER 3 Mechanism studies of intramolecular C‒H activation 18 3-1 Synthesis of carbodicarbene (CDC) 18 3-2 Synthesis and characterization of C1-CDC‒Ni(II), C2-CDC‒Ni(II) complexes 21 3-3 Mechanism studies of intramolecular C‒H activation 25 3-3-1 Literature review of C‒H bond activation 25 3-3-2 Observation of CDC‒Ni(I) complexes during synthesis of CDC‒Ni(II) complexes 28 3-3-3 Proposed mechanisms 29 3-3-4 Synthesis of C1-CDC‒Ni(I), C2-CDC‒Ni(I) complexes 31 3-3-5 Kinetic isotope effect (KIE) experiments 32 3-3-6 Time-tracking experiments 35 3-3-7 Formation of complex CDC‒Ni(II) under different equivalents of CDC 37 3-3-8 Replacement of 2nd equivalent of CDC with other bases 42 3-4 Conclusion 43 CHAPTER 4 Investigation of the redox activity of CDC in different metal complexes 45 4-1 Introduction 45 4-2 Synthesis of CDC-NHC-based Ni(II) and Pd(II) complexes 45 4-3 Probing the redox properties of CDC-NHC-based Ni(II) and Pd(II) complexes 46 4-4 Synthesis of oxidized species of CDC-NHC-based Ni(II) and Pd(II) complexes 49 4-5 Crystallographic characterization 50 4-6 X-ray absorption spectroscopy (XAS) studies 54 4-7 Electron paramagnetic resonance (EPR) spectroscopy 56 4-8 Conclusion 59 CHAPTER 5 Experimental Section 60 5-1 General considerations 60 5-1-1 General techniques 60 5-2-2 Solvents and reagents 60 5-2-3 Literature search 61 5-2 NMR spectroscopy 61 5-3 Mass spectrometry 63 5-4 X-ray crystal structure determination 63 5-5 EPR spectroscopy 63 5-6 X-ray absorption spectroscopy 63 5-7 Cyclic voltammetry 64 5-8 Synthesis 65 5-9 Formation of complex CDC‒Ni(II) under different equivalents of CDC 97 5-10 EPR calibration curves 98 CHAPTER 6 Reference 101 Appendix 113 7-1 NMR spectra 113 7-2 EPR spectra 135 7-3 Single crystal X-ray diffraction data 140 | - |
| dc.language.iso | en | - |
| dc.title | 探討同碳雙碳烯與鎳金屬進行分子內碳‒氫活化反應機制及研究其錯合物之氧化還原活性 | zh_TW |
| dc.title | Mechanism Studies of Intramolecular C(sp3)‒H Activation in Carbodicarbene-Nickel Complexes and Investigation of Their Redox Activity | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 112-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 劉如熹;方頡睿;蔡福裕 | zh_TW |
| dc.contributor.oralexamcommittee | Ru-Shi Liu;Jeffery M. Farrell;Fu-Yu Tsai | en |
| dc.subject.keyword | 同碳雙碳烯,鎳金屬,碳－氫活化反應,氧化還原, | zh_TW |
| dc.subject.keyword | Carbodicarbene,nickel,C‒H activation,redox activity, | en |
| dc.relation.page | 151 | - |
| dc.identifier.doi | 10.6342/NTU202403637 | - |
| dc.rights.note | 未授權 | - |
| dc.date.accepted | 2024-08-09 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| 顯示於系所單位： | 化學系 | |
文件中的檔案：
| 檔案 | 大小 | 格式 | |
|---|---|---|---|
| ntu-112-2.pdf 未授權公開取用 | 11.12 MB | Adobe PDF |
系統中的文件，除了特別指名其著作權條款之外，均受到著作權保護，並且保留所有的權利。