請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/56210
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 劉緒宗(Shiuh-Tzung Liu) | |
dc.contributor.author | Chia-Han Lee | en |
dc.contributor.author | 李佳翰 | zh_TW |
dc.date.accessioned | 2021-06-16T05:19:04Z | - |
dc.date.available | 2016-08-21 | |
dc.date.copyright | 2014-08-21 | |
dc.date.issued | 2014 | |
dc.date.submitted | 2014-08-17 | |
dc.identifier.citation | (1) Waldron, K. J.; Robinson, N. J. Nat. Rev. Microbiol. 2009, 6, 25-35.
(2) Whittington, D. A.; Lippard, S. J. J. Am. Chem. Soc. 2001, 123, 827-838. (3) Benini, S.; Rypniewski, W. R.; Wilson, K. S.; Miletti, S.; Ciurli, S.; Mangani, S. Structure. 1999, 7, 205-216. (4) Fox, S.; Nanthakumar, A.; Wei, N.; Murthy, N. N.; Karlin, K. D. Pure & Appl. Cherm. 1993, 65, 2335-2342. (5) Shu, L.; Nesheim, J. C.; Kauffmann, K.; Munck, E.; Lipscomb, J. D.; Que, L. Jr. Science 1997, 275, 515-518. (6) Magnus, K. A.; Ton-That, H.; Carpenter, J. E. Chem. Rev. 1994, 94, 727-735. (7) Park, J.; Hong, S. Chem. Soc. Rev. 2012, 41, 6931–6943. (8) Liao, B.-S.; Liu, Y.-H.; Peng, S.-M.; Liu, S.-T. Dalton Trans. 2012, 41, 1158–1164. (9) DiMauro, E. F.; Kozlowski, M. C. Org. Lett. 2001, 3, 3053–3056. (10) Ooi, T.; Takahashi, M.; Yamada, M.; Tayama, E.; Omoto, K.; Maruoka, K. J. Am. Chem. Soc. 2004, 126, 1150-1160. (11) Powers, D. C.; Benitez, D.; Tkatchouk, E.; Goddard III, W. A.; Ritter, T.; J. Am. Chem. Soc. 2010, 132, 14092–14103. (12) Bratko, I.; Gomez, M. Dalton Trans. 2013, 42, 10664-10681. (13) Tikkanen, W. R.; Kruger, C.; Bomben, K. D.; Jolly, W. L.; Kaska, W. C.; Ford, P. C. Inorg. Chem. 1984, 23, 3633-3638. (14) (a) He, C.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 184-185. (b) He, C.; Barrios, A. M.; Lee, D.; Kuzelka, J.; Davydov, R. M.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 12683–12690. (c) He, C.; DuBois, J. L.; Hedman, B.; Hodgson, K. O.; Lippard, S. J. Angew. Chem. Int. Ed. Engl. 2001, 40, 1484-1487. (d) He, C.; Lippard, S. J. Inorg. Chem. 2000, 39, 5225-5231. (15) Cheng, T.-P.; Liao, B.-S.; Liu, Y.-H.; Peng, S.-M.; Liu, S.-T. Dalton Trans. 2012, 41, 3468-3473. (16) (a) Angaridis, P. Ruthenium Compounds. In Multiple Bonds Between Metal Atoms, 3rd ed.; Cotton, F. A.; Murillo, C. A.; Walton, R. A., Ed.; Springer: New York, 2005; p 377. (b) Angaridis, P. Ruthenium Compounds. In Multiple Bonds Between Metal Atoms, 3rd ed.; Cotton, F. A.; Murillo, C. A.; Walton, R. A., Ed.; Springer: New York, 2005; p 384. (c) Angaridis, P. Ruthenium Compounds. In Multiple Bonds Between Metal Atoms, 3rd ed.; Cotton, F. A.; Murillo, C. A.; Walton, R. A., Ed.; Springer: New York, 2005; pp 404–405. (d) Angaridis, P. Ruthenium Compounds. In Multiple Bonds Between Metal Atoms, 3rd ed.; Cotton, F. A.; Murillo, C. A.; Walton, R. A., Ed.; Springer: New York, 2005; p 414. (17) Norman Jr. J. G.; Kolari, H. J. J. Am. Chem. Soc. 1978, 100, 791-799. (18) Lindsay, A. J.; Tooze, R. P.; Motevalli, M.; Hursthouse, M. B.; Wilkinson, G.; J. Chem. Soc., Chem. Commun. 1984, 1383. (19) Lindsay, A. J.; Wilkinson, G.; Motevalli, G.; Hursthouse, M. B. J. Chem. Soc., Dalton. Trans. 1985, 2321. (20) (a) Duan, L.; Xu, Y.; Tong, L.; Sun, L. ChemSusChem 2011, 4, 238-244. (b) Duan, L.; Fischer, A.; Xu, Y.; Sun, L. J. Am. Chem. Soc. 2009, 131, 10397-10399. (c) Tong, L.; Duan, L.; Xu, Y.; Privalov, T.; Sun, L. Angew. Chem. 2011, 123, 72, 465-469. (d) Tong, L.; Lele Duan, Xu, Y.; Privalov, T.; Sun, L. (d) Tong, L.; Lele Duan, Xu, Y.; Privalov, T.; Sun, L. Angew. Chem. Int. Ed. 2011, 50, 445-449. (21) Hetterscheid, D. G. H.; Reek, J. N. H. Angew. Chem. Int. Ed. 2012, 51, 9740 – 9747. (22) Tong, L.; Duan, L.; Xu, Y.; Privalov, T.; Sun, L. Angew. Chem. Int. Ed. 2011, 50, 445 –449. (23) Criegee R. Angew. Chem. Int. Ed. 1975, 14, 745-752. (24) Garti, N.; Avni, E. Colloids Surf. 1982, 4, 33–41. (25) (a) Warwel, S.; Klass, M. R. gen. Lipid Technol. 1997, 10–14. (b) Klass, M. R. gen.; Bavaj, P.; Warwel, S. Fat Sci. Technol. 1995, 97, 359–367. (26) (a) Santacesaria, E.; Sorrentino, A.; Rainone, F.; Di Serio, M.; Speranza, F. Ind. Eng. Chem. Res. 2000, 39, 2766–2771; (b) Santacesaria, E.; Ambrosio, M.; Sorrentino, A.; Tesser, R.; Di Serio, M. Catal. Today 2003, 79–80, 59–65; (c) Oakley, M. A.; Woodward, S.; Coupland, K.; Parker, D.; Temple-Heald, C. J. Mol. Catal. A: Chem. 1999, 150, 105–111; (d) Antonelli, E.; D_Aloisio, R.; Gambaro, M.; Fiorani, T.; Venturello, C. J. Org. Chem. 1998, 63, 7190–7206. (27) Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981,46, 3936-3938. (28) Djerassi, C.; Engle, R. R. J. Am. Chem. Soc. 1953, 75, 3838-3840. (29) Plietker, B.; Niggemann, M. Org. Lett. 2003, 5, 3353-3356. (30) Cotton, F. A.; Norman, J. G.; Spencer, A.; Wilkinson, G. Chem. Comm. 1971, 967-968. (31) Zimmermann, F.; Meux, E.; Mieloszynski, J. L.; Lecuire, J. M.; Oget, N. 73 Tetrahedron Lett. 2005, 46, 3201-3203. (32) Aghabozorg, H.; Palenik, R. C.; Palenik, G. J. Inorg. Chem. 1985, 24, 4214-4216. (33) Vu, C.; Walker, D.; Wells, J.; Fox, S. J. Heterocyclic Chem. 2002, 39, 829-832. (34) Cavanaugh, M. A.; Cappo, V. M.; Alexander, C. J.; Good, M. L. Inorg. Chem. 1976, 15, 2615-2621. (35) Somphon, W.; Haller, K, J. J. Cryst. Growth. 2013, 362, 252-258. (36) Bino, A.; Cotton, F. A.; Felthouse, T. R. Inorg. Chem. 1979, 18, 2599-2604. (37) 廖倍偲 國立台灣大學化學系博士論文-金屬紫質與雙金屬錯合物之合成與 催化活性, 2012. (38) Diez, J.; Gamasa, P.; Gimeno, J.; Lanfranchi, M.; Tiripicchio, A. J. Chem. Soc. Dalton Trans. 1990, 1027-1033. (39) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. J. Chem. Soc. Perkin Trans. 2. 1987, S1-S19. (40) Karlin, K. D.; Dahlstrom, P. L.; Stanford, M. L.; Zubieta, J. J. C.S. Chem. Comm. 1979, 465-467. (41) Slater, J. C. J. Chem. Phys. 1964, 41, 3199. (42) Zuo, J. M.; Kim, M.; O'Keeffe, M.; Spence, J. C. H. Nature, 1999, 401, 49-52. (43) (a) Diez, J.; Gamasa, M. P.; Gimeno, J. J. Chem. Soc. Dalton Trans. 1987, 1275-1278. (b)Yam, V. W.-W.; Lee, W.-K.; Lai, T. F. Organometallics. 1993, 12, 2383-2387. (c)Yam, V. W.-W.; Lam, C.-H.; Cheung, K. K. Chem. Commun. 2001, 37, 545–546. (44) (a)Jansen, M. Angew Chem. Int. Ed. Engl. 1987, 26, 1098-1110 (b) Zuo, J. M.; 74 Kim, M.; O'Keeffe, M.; Spence, J. C. H. Nature, 1999, 401, 49-52. (45) Chen, Y.; Chen, J.-S.; Gan, X.; Fu, W.-F. Inorg. Chim. Acta. 2009, 362. 2492–2498. (46) Takusagawa, F.; Shimada, A. Chem. Lett. 1973, 2, 1089–1090. (47) (a)Campos-Fernandez, C. S.; Ouyang, X.; Dunbar, K. R. Inorg. Chem. 2000, 39, 2432-2433. (b)Binamira-Soriaga, E.; Keder, N. L.; Kaska, W. C. Inorg. Chem. 1990, 29, 3167-3171. (48) De Villiers, J. P. R.; Boeyens, J. C. A. J. Cryst. Mol. Struct. 1975, 5, 215-226. (49) Norman, Jr. J. G.; Renzoni, G. E.; Case, D. A. J. Am. Chem. Soc. 1979, 101, 5256-5267. (50) Collin, J.-P.; Jouaiti, A.; Sauvage, J.-P.; Kaska, W. C.; McLoughlin, M. A.; Keder, N. L.; Harrison, W. T. A.; Stucky, G. D. Inorg. Chem. 1990, 29, 2238-2241. (51) Jones, N. D.; James, B. R. Adv. Synth. Catal. 2002, 344, 1126-1134. (52) (a) Panda, R.; Panigrahi, A. K.; Patnaik, C.; Sahu, S. K.; Mahapatra, S. K. Bull. Chem. Soc. Jpn. 1988, 61, 1363-136 7. (b) Hassall, C. H. Org. React. 1957, 9, 73-106. (53) Saisaha, P.; Buettner, L; Van Der Meer, M.; Hage, R.; Feringa, B. L.; Browne, W. R.; de Boer, J. W. Adv. Synth. Catal. 2013, 355, 2591–2603. (54) Shimada, Y.; Hattori, K.; Tada, N.; Miura, T.; Itoh, A. Synthesis, 2013, 45, 2684-2688. (55) She, M.-Y.; Xiao, D.-W.; Yin, B.; Yang, Z., Liu, P.; Li, J.-L.; Shi, Z. Tetrahedron, 2013, 69, 7264-7268. (56) Hronowski, L. J. J.; Szare, W. A. Can. J. Chem. 1988, 66, 61-70. 75 (57) Matsusaki, Y.; Yamaguchi, T.; Tada, N.; Miura, T.; Itoh, A. Synlett, 2012, 23, 2059-2062. (58) Roberto, B.; Enrico, M.; Marino, P.; Goffredo, R. Synthesis, 1988, 11, 915–917. (59) Behjat, B.; Majid, M.; Abbas, R.; Shahram, T.; Valiollah, M.; M.-B. Synlett, 2013, 24, 90–96. (60) Wang, W.; Zhang, G.; Lang, R.; Xia, C.; Li, F. Green Chem. 2013, 15, 635-640. (61) Zhou, L.; Liu, X.; Ji, J.; Zhang, Y.; Hu, X.; Lin, L.; Feng, X. J. Am. Chem. Soc. 2012, 134, 17023–17026. (62) Kantam, M. L.; Kishore, R.; Yadav, J.; Sudhakar, M.; Venugopal, A. Adv. Synth. Catal. 2012, 354, 663–669. (63) Vu, C.; Walker, D.; Wells, J.; Fox, S.; J. Heterocyclic Chem. 2002, 39, 829-832. (64) Ivanović, I.; Grgurić-śipka, S.; Gligorijević, N.; Radulović, S.; Roller, A.; Tešić, Ž.; Keppler, B, K. J. Serb. Chem. Soc. 2011, 76, 53–61. (65) (a) The Range of Chemical Shifts, Coupling Constants, and What Influences Each. In Phosphorus-31 NMR Spectroscopy; Kuhl, O., Ed.; Springer: Heidelberg, 2008, p 19. (b) Low, P. M. N.; Yong, Y. L.; Yan, Y. K.; Hor, T. S. A. Organometallics. 1996, 15, 1369-1375. (66) Kang, S.; Joo, C.; Kim, S. M.; Han, H.; Yang, J. W. Tetrahedron Lett. 2011, 52, 502–504. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/56210 | - |
dc.description.abstract | 雙核金屬催化劑被證明於催化系統中存在特殊活性,過去文獻中已有許多例子說明兩個金屬離子於催化過程中的協同效應。多牙配體的設計直接影響到金屬之配位環境與離子間距,這些性質同時也決定協同效應發生的機會,因此製備能裝載多金屬離子之多牙配基成為火紅的研究題材。
在本篇論文中,利用1, 8-萘啶- 2, 7-雙羧酸根配體(1,8-naphthyridine-2,7-dicarboxylate)做為多牙配基,且將其與銅、鈷與釕金屬配位形成錯合物Cu2(I, I)、[Co2(II, II)]2 與Ca[Ru2(II, II)]2,鑑定其晶體結構並討論其性質。萘啶羧酸根配基兩側之氮氧配體分別與三種金屬離子 形成兩組金屬五元環,多價負離子型配體除了與金屬配位能力良好外,還可穩定高價態金屬中心,且也因羧酸根與質子性分子之氫鍵作用力,使此系列錯合物可溶解於水、甲醇和乙醇等質子極性溶劑。 烯基氧化裂解反應於化學工業上多使用臭氧化反應進行,但化學家仍不斷找尋更環保且高效之替代方案,而釕金屬催化系統正活躍於該舞台。於過去文獻中,釕金屬催化之烯基氧化裂解反應常選用有機溶劑與水的共溶劑系統,本研究使用雙核釕金屬催化劑Ca[Ru2(II, II)]2 於水中進行此催化,發現其反應性十分良好,動力學曲線分析也說明雙核結構的確對烯基氧化裂解反應有助益。 | zh_TW |
dc.description.abstract | Dimetallic complexes are known to have unique properties in transition metal catalyzed reactions, and there are a lot of examples proving the cooperation between metals during the catalysis. Therefore, there is a need to design and synthesis of multi-dentate ligands for construction of dimetallic systems.
In this research, 1,8-naphthyridine-2,7-dicarboxylate was used as the multi-dentate ligand for complexation with ruthenium, copper and cobalt ions to form Cu2(I, I), [Co2(II, II)]2 and Ca[Ru2(II, II)]2. Moreover, we successfully disclosed their absolute structures by crystals. Naphthyridine dicarboxylate ligand can capture two metal ions to form two five-member rings with N and O donors. Such a dicarboxylate ligand not only has strong coordinating ability but also stabilizes metal centers with high oxidation state. Because of the H-bonding interaction between carboxylate groups and protic molecules, the ligand readily assists the solubility of the resulting complexes in protic solvents like water, methanol and ethanol. Industrial application on oxidative cleavage of olefins usually go through ozonolysis. However, chemists are still looking for environmental-friendly alternatives with higher efficiency. In the past, ruthenium-catalyzed oxidative cleavage reaction usually works in water-organic co-solvent system. Surprisingly, Ca[Ru2(II, II)]2 can catalyzed this reaction in water with great performance. Kinetic experiment also suggests that binuclear structure really assists the cleavage reaction. | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T05:19:04Z (GMT). No. of bitstreams: 1 ntu-103-R01223177-1.pdf: 7288838 bytes, checksum: 5e7ca0f7a622f4188671f614a7c73b71 (MD5) Previous issue date: 2014 | en |
dc.description.tableofcontents | 論文摘要................................................... I
Abstract ................................................ II 第一章 緒論 ............................................... 1 第一節 雙核金屬之協同效應 .................................... 1 第二節 雙釕paddlewheel 結構與多價陰離子型配基 .................. 6 第三節 烯基氧化裂解反應 ...................................... 9 第四節 研究目的 ........................................... 13 第二章 配位基及其金屬錯合物之合成 ............................. 14 第一節 雙羧酸萘啶配位基的合成 ................................ 14 第二節 化合物3 之雙銅、雙鈷及雙釕金屬錯合物;合成及結構鑑定 ....... 16 第三章 雙核釕金屬錯合物於催化氧化之應用 ........................ 45 第一節 釕金屬催化之氧化裂解反應 – 最佳化反應條件 ................ 45 第二節 不同釕金屬催化劑於氧化裂解之表現 ........................ 48 第三節 氧化裂解反應之適用性 ................................. 50 第四節 推測之反應機制....................................... 54 第四章 結論 .............................................. 57 第五章 實驗部份 ........................................... 58 第一節 測試及實驗儀器....................................... 58 第二節 試劑來源與前處理 ..................................... 59 第三節 化合物之合成 ........................................ 60 第四節 烯基氧化裂解反應 ..................................... 65 參考文獻 ................................................. 70 附錄一 配位基與金屬錯合物之光譜資料 ........................... 76 附錄二 化合物之光譜資料 ..................................... 88 附錄三 錯合物之晶體資料 .................................... 101 | |
dc.language.iso | zh-TW | |
dc.title | 萘啶雙羧酸根配體之過渡金屬錯合物的合成與催化探討 | zh_TW |
dc.title | Syntheses of Transition Metal Complexes Containing a Naphthyridine Dicarboxylate Ligand and Catalytic Activity Study | en |
dc.type | Thesis | |
dc.date.schoolyear | 102-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 詹益慈(Yi-Tsu Chan),陳竹亭(Jwu-Ting Chen) | |
dc.subject.keyword | ?啶,雙金屬,羧酸根, | zh_TW |
dc.subject.keyword | naphyridine,dimetallic,carboxylate, | en |
dc.relation.page | 124 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2014-08-17 | |
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 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-103-1.pdf 目前未授權公開取用 | 7.12 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。