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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯 | |
| dc.contributor.author | Yun-Ting Wang | en |
| dc.contributor.author | 王韻婷 | zh_TW |
| dc.date.accessioned | 2021-06-16T13:26:24Z | - |
| dc.date.available | 2023-12-31 | |
| dc.date.copyright | 2013-07-30 | |
| dc.date.issued | 2013 | |
| dc.date.submitted | 2013-07-23 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/62075 | - |
| dc.description.abstract | 近年來橋接式的多芽氮異環碳烯受到許多的注目，因為他們具有極大的潛力建構有機金屬聚合物亦或是同元聚合物。致力於拓展這個領域，我們以具有高度對稱性和特定角度的分子三亞苯為基本骨架，設計並合成一系列具有不同氮取代基的平面三牙咪唑鹽 (4a-c and 5d-e)。當取代基為1,1-二甲基乙基和1,3,5-三甲苯時，藉由簡單的脫氫反應可得到穩定的氮異環碳烯，進而可與金屬前驅物反應生成相對應的三核金的金屬錯合物 (6a-(AuCl)3, 7a-(Au(DMAP)3(PF6)3 and 7b-(AuCl)3)。此外，4b 直接與乙酸銀進行金屬化反應也可以得到三核銀的金屬錯合物 (7b-(AgOAc)3)。若是取代基為二苯甲烷和正丁基時，一系列的三核金屬錯合物包括(5c-(Rh(COD)Cl)3, 6e-(AgOAc)3, 7e-(Hg(OAc)2)3, 8e-(Ni(Cp)I)3和 9e-(Rh(COD)Cl)3)皆可直接藉由三芽咪唑鹽與相對應的金屬前驅物反應得到。此外，我們也合成出帶有銀金屬(8a: R = tert-butyl; 6c: R = diphenylmethyl)，鈀金屬(9a: R = tert-butyl)和金金屬(10a: R = tert-butyl)的有機金屬聚合物，以期橋接式的多芽氮異環碳烯能在以有機金屬為主體之延伸性材料的建構及異相催化上能有更進一步的發展。 | zh_TW |
| dc.description.abstract | Bridging type poly-N-heterocyclic carbenes have attracted much attention recently because of their potential applications in constructing organometallic polymers or homopolymers. In order to contribute to this field, we designed and synthesized a series of planar tris-imidazolium salts with various N-substituents, based on the highly symmetric and angular triphenylene backbone (4a-c and 5d-e). With t-butyl and mesityl substituents, free tris-NHCs could be generated and isolated via deprotonation, and further reacted with metal precursors to afford the corresponding tri-nuclear gold complexes (6a-(AuCl)3, 7a-(Au(DMAP)3(PF6)3 and 7b-(AuCl)3). Direct metalation of 4b with AgOAc gave the tri-Ag complex (7b-(AgOAc)3). For the diphenylmethyl (4c) and n-butyl (5e) substituted ones, tri-nuclear metal complexes (5c-(Rh(COD)Cl)3, 6e-(AgOAc)3, 7e-(Hg(OAc)2)3, 8e-(Ni(Cp)I)3, and 9e-(Rh(COD)Cl)3) could also be isolated by direct metalation when treated with appropriate metal precursors. In addition, the Ag-NHC (8a: R = tert-butyl; 6c: R = diphenylmethyl) and Au-NHC (9a: R = tert-butyl) organometallic polymers have been synthesized and investigated as well. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T13:26:24Z (GMT). No. of bitstreams: 1 ntu-102-R00223170-1.pdf: 10499689 bytes, checksum: f67e9d3aa0018c14f814e9d77e969339 (MD5) Previous issue date: 2013 | en |
| dc.description.tableofcontents | 口委審定書……………………………………………………………………………...
謝誌 i 摘要 ii ABSTRACT iii CONTENTS iv LIST OF FIGURES vi LIST OF SCHEMES ix LIST OF TABLES xi Chapter 1 Introduction and Research Objective 1 1.1 History and properties of N-heterocyclic carbenes (NHCs) 1 1.2 Poly NHCs 6 1.3 NHCs as building blocks in metal – directed supramolecular chemistry 11 1.4 Research objective 13 Chapter 2 Triphenylene-Based Tris-N-Heterocyclic Carbene 14 2.1 Ligand design 14 2.2 Result and discussion 15 2.2.1 Tris(imidazolium) salts with bulky N-substituents 15 2.2.2 Tris(imidazolium) salt with small N-substituents 18 2.2.3 Synthesis and characterization of free tris(NHC)s 20 Chapter 3 Trimetallic complexes of Triphenylene-Based Tris-(NHC)s 23 3.1 Synthesis and characterization of t-butyl-tris(NHC) metal complexes 23 3.2 Synthesis and characterization of mesityl-tris(NHC) metal complexes 28 3.3 Synthesis and characterization of diPhMe-tris(NHC) metal complex 31 3.4 Synthesis and characterization of n-butyl-tris(NHC) metal complexes 32 Chapter 4 NHC as building block in coordination polymer 38 4.1 Coordination polymer composed of tris-NHCs and metal 39 4.2 Coordination polymer composed of tris-NHC-M complex and bipyridine 42 4.3 Homopolymer composed of n-butyl tris(NHC) 45 Chapter 5 Conclusion 46 Chapter 6 Experimental section 48 Chapter 7 Reference 65 Chapter 8 Appendix 68 | |
| dc.language.iso | en | |
| dc.subject | 有機金屬聚合物 | zh_TW |
| dc.subject | 三亞苯 | zh_TW |
| dc.subject | 三芽咪唑鹽 | zh_TW |
| dc.subject | 氮異環碳烯 | zh_TW |
| dc.subject | 金屬錯合物 | zh_TW |
| dc.subject | trisimidazolium | en |
| dc.subject | organometallic polymer | en |
| dc.subject | metal complex | en |
| dc.subject | triphenylene | en |
| dc.subject | N-heterocyclic carbene | en |
| dc.title | 三芽氮異環碳烯與其金屬化合物之合成與鑑定 | zh_TW |
| dc.title | Syntheses of Tris-N-Heterocyclic Carbenes and Their Corresponding Coordination Complexes & Polymers | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 101-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 林英智,王朝諺 | |
| dc.subject.keyword | 三亞苯,三芽咪唑鹽,氮異環碳烯,金屬錯合物,有機金屬聚合物, | zh_TW |
| dc.subject.keyword | triphenylene,trisimidazolium,N-heterocyclic carbene,metal complex,organometallic polymer, | en |
| dc.relation.page | 197 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2013-07-23 | |
| 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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