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請用此 Handle URI 來引用此文件: http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57521
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dc.contributor.advisor邱靜雯(Ching-Wen Chiu)
dc.contributor.authorChung-Hao Huen
dc.contributor.author胡忠豪zh_TW
dc.date.accessioned2021-06-16T06:49:44Z-
dc.date.available2019-07-29
dc.date.copyright2014-07-29
dc.date.issued2014
dc.date.submitted2014-07-24
dc.identifier.citation(1) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem. Rev. 1999, 100, 39.
(2) Wanzlick, H. W.; Kleiner, H. J. Angew. Chem. 1961, 73, 493.
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(5) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953.
(6) Gstottmayr, C. W. K.; Bohm, V. P. W.; Herdtweck, E.; Grosche, M.; Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1363.
(7) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791.
(8) Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361.
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(10) Hahn, F. E.; Jahnke, M. C. Angew. Chem. Int. Ed. 2008, 47, 3122.
(11) Crudden, C. M.; Allen, D. P. Coord. Chem. Rev. 2004, 248, 2247.
(12) Oisaki, K. L., Q.; Furukawa, H.; Czaja, A. U.; Yaghi, O. M. J. Am. Chem. Soc. 2010, 132, 9262.
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(15) Kong, G. Q.; Xu, X.; Zou, C.; Wu, C. D. Chem. Commun. 2011, 47, 11005.
(16) Choi, J.; Yang, H. Y.; Kim, H. J.; Son, S. U. Angew. Chem. Int. Ed. 2010, 49, 7718.
(17) Boydston, A. J.; Williams, K. A.; Bielawski, C. W. J. Am. Chem. Soc. 2005, 127, 12496.
(18) Williams, K. A.; Boydston, A. J.; Bielawski, C. W. Chem. Soc.Rev. 2007, 36, 729.
(19) Khramov, D. M.; Boydston, A. J.; Bielawski, C. W. Org. Lett. 2006, 8, 1831.
(20) Kamplain, J. W.; Bielawski, C. W. Chem. Commun. 2006, 1727.
(21) Karimi, B.; Akhavan, P. F. Chem. Commun. 2009, 3750.
(22) Wang, Y. T.; Chang, M. T.; Lee, G. H.; Peng, S. M.; Chiu, C. W. Chem. Commun. 2013, 49, 7258.
(23) Rit, A.; Pape, T.; Hahn, F. E. J. Am. Chem. Soc. 2010, 132, 4572.
(24) Hahn, F. E.; Radloff, C.; Pape, T.; Hepp, A. Chem. Eur. J. 2008, 14, 10900.
(25) Su, J. H.; Lee, G. H.; Peng, S. M.; Chiu, C. W. Dalton Trans. 2014, 43, 3059.
(26) Chen, Y. H. (2013). Syntheses of Poly N-Heterocyclic Carbene by Assembly Approach.Unpublished master's thesis, National Taiwan University, Taipei, ROC.
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dc.identifier.urihttp://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57521-
dc.description.abstract自從1991年氮異環碳烯 (NHC) 第一次被Ardruengo成功地合成出來,氮異環碳烯已經被廣泛地應用於各種不同的領域中。由於其優異的穩定性與電子提供能力,氮異環碳烯常被應用於金屬催化劑的配基選擇,並使這種催化劑有著顯著的催化能力。近年來,科學家積極地研究多氮異環碳烯與超分子結構兩種領域的結合。我們團隊設計了一種雙官能基的配基,一端是碳烯前驅物的咪唑官能基,而另一端是金屬連結端的羧基官能基。當這樣的配基成功地與親氧性金屬鍵結,則這樣的多咪唑錯合物就可以成功地合成出來,並且這樣的錯合物可以進一步與其他的金屬鍵結形成網狀結構。在我們得實驗中,我們成功的合成出一個以鈷連結的雙咪唑錯合物與一個以鋅連結的四咪唑錯合物。除此之外,我們意外的合成出一個以兩個銅原子為骨幹的網狀結構,而這樣的結構,它的配基已從原本的咪唑配基氧化為咪唑啉酮 (imidazolidinone)。並且我們也製作一個亞乙基硫脲 (imidazolidinethion) 的配基,利用這樣的配基,我們成功地做出一個四個分支的錯合物,並且這樣的錯合物是與之前的網狀結構單體是非常的相似。zh_TW
dc.description.abstractSince the publication of the first N-heterocyclic carbene (NHC) by Ardruengo’s group in 1991, NHCs have been widely used in several fields. Due to their electron donating ability and good stability, NHC containing organometallic catalysts generally possess superb catalytic performances. Recently, poly-dentate NHC ligands have drawn much attention for their potential application in organometallic supramolecules. To contribute to the poly-NHC field, we have synthesized a bifuctional ligand, which contains a carboxylate moiety and an imidazolium unit to serve as the metal coordination site and the carbene precursor, respectively. When the bifuctional ligand coordinates to the oxophilic metal centers, multikis imidazolium salts, which could function as bridging ligands for framework materials, are expected. To this end, we successfully synthesized a Co(II) linked bis-imidazolium salt and a Zn(II) connected tetrakis-imidazolium salt. Furthermore, a Cu(II) linked tetra-imidazolinethione complex, and a Cu(II) based tetradentate ligand, which was oxidized to form an imidazolidinone coordinated extended structure, were also synthesized.en
dc.description.provenanceMade available in DSpace on 2021-06-16T06:49:44Z (GMT). No. of bitstreams: 1
ntu-103-R01223169-1.pdf: 5981302 bytes, checksum: 4b83d2497ecb2e407e499950737d856a (MD5)
Previous issue date: 2014
en
dc.description.tableofcontents中文摘要 I
Abstract II
Chapter 1 Introduction 1
1.1 N-Heterocyclic carbene (NHC) 1
1.1.1 Definition and Characteristics 1
1.1.2 History 2
1.2 N-Heterocyclic Carbene in Supramolecules 3
1.3 Syntheses of Poly-NHCs 6
1.3.1 Stepwise Synthesis 6
1.3.2 Assembly 8
Chapter 2 Results and Discussions 11
2.1 Concept 11
2.2 Syntheses of NHC ligands 12
2.2.1 Syntheses of organic ligand 2, 4, 5 12
2.3 Assembly with transition metal salts 15
2.3.1 Reaction of 2 with CoCl2 15
2.3.2 Reaction of 4 with Zn(ClO4)2 16
2.3.3 Reaction of 4 with Cu(NO3)2 19
2.3.4 Reaction of 5 with Cu(NO3)2 23
Chapter 3 Conclusions 25
Chapter 4 Experimental section 26
Chapter 5 References 34
Appendix 36
Crystal Data 36
NMR spectrums 81
dc.language.isoen
dc.subject氮異環碳烯zh_TW
dc.subject金屬有機網狀聚合物zh_TW
dc.subject超分子化合物zh_TW
dc.subjectN-Heterocyclic carbeneen
dc.subjectMetal-organic frameworken
dc.subjectsupramoleculeen
dc.title咪唑-羧基化合物的配位化學zh_TW
dc.titleCoordination Chemistry of Imidazolium-Carboxylate Liganden
dc.typeThesis
dc.date.schoolyear102-2
dc.description.degree碩士
dc.contributor.oralexamcommittee詹益慈(Yi-Tsu Chan),鄭淑芬(Soofin Cheng)
dc.subject.keyword氮異環碳烯,金屬有機網狀聚合物,超分子化合物,zh_TW
dc.subject.keywordN-Heterocyclic carbene,Metal-organic framework,supramolecule,en
dc.relation.page88
dc.rights.note有償授權
dc.date.accepted2014-07-24
dc.contributor.author-college理學院zh_TW
dc.contributor.author-dept化學研究所zh_TW
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