氮異環碳烯化合物之銀、銅、鎳、鈀金屬錯合物
合成與相關催化應用探討

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姓名

劉雅銘(Ya-Ming Liu) 查詢紙本館藏

畢業系所

化學學系

論文名稱

氮異環碳烯化合物之銀、銅、鎳、鈀金屬錯合物合成與相關催化應用探討
(Synthesis and Characterization of 4-Picolyl-Linked NitrogenHeterocyclic Carbene Complexes and Their Application TowardMizoroki-Heck Coupling and C-B Bond Formation )

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摘要(中)

最近幾年，氮異環碳烯咪與金屬錯合物在催化的應用方面已被廣泛的發展。在本研究中，我們首先合成一系列新穎的氮異環碳烯咪唑鹽類，其側邊臂上具有含氮配位基，並成功地將咪唑鹽類與氧化銀反應，順利合成穩定的Ag-NHC 錯合物2。接著，藉由這些錯合物進行金屬置換反應，進而得到Cu-NHC 錯合物3以及Pd-NHC 錯合物，在此，我們也嘗試利用咪唑鹽類直接合成Ni-NHC 錯合物及Pd-NHC 錯合物；並且經由核磁共振、質譜分析、單晶X-ray 繞射分析達到結構的確立以及呈現出分子內部彼此互相影響的結果。此外，我們將所合成的 Pd-NHC 錯合物做為催化試劑，進行一系列的Mizoroki-Heck 偶合反應探討，結果顯示，在低劑量的催化劑下極有相當好的產率。然而我們也將催化劑應用於多苯環的系統，屬於材料的合成方面的應用。幸運地，我們也同樣可以得到相當不錯的催化效果，其中包含高度的位向選擇性。最後我們利用合成的Cu-NHC 錯合物當作催化劑，應用在碳硼鍵的生成，並希望合成此具有高度反應性的含硼官能基化合物，能有助於我們更進一步應用於其他合成方面。

摘要(英)

N-heterocyclic carbenes (NHCs) are widely utilized as ligand in homogeneous transitional metal as well as catalyst in asymmetry organocatalysis, therefore, we have
prepared a series of novel imidazolium salts precursors for 4-picolyl-linked N-heterocyclic carbene ligands. These imidazolium salts can successfully react with Ag2O to afford air-stable silver carbene complexes 2. Silver carbene complexes 2 can then act as a carbene transfer agent for the synthesis of copper carbene complexes 3 or
palladium carbene complexes by a base. We also attempt to prepare the nickel and palladium complexes from the imidazolium salts. These complexes have been characterized by multinuclear (1H, 13C) NMR spectroscopy, MS measurements and identity of those complexes are confirmed by single-crystal X-ray diffraction. In addition, we investigate the palladium carbene complexes catalyzed Heck
reaction and proved these palladium carbene complexes shows promising activity, and the results have validated the importance of the cooperating effect invoked by
pyridine moiety to assist the efficiency of this catalysis. Next, we examined the coupling of styrene with fused aromatic rings system and excellent conversion was
observed for this system. Finally, we carried out the hydroboration catalysis using copper carbene complexes of 3 and have good yield. These studies of these highly functionalized compounds allowed us to develop broader applicability in the synthetic methodologies.

關鍵字(中)

★ 氮異環碳烯化合物

關鍵字(英)

★ Carbene

論文目次

Contents
Abstract (Chinese) I
Abstract (English) II
Acknowledgement (Chinese) III
Contents V
List of Figures VII
List of Schemes VIII
List of Tables IX
Chapter 1 Introduction……………...…………………………………………...1
1.1 What is Carbene……………………………………………...………………..1
1.2 What is NHC Carbene………………………………………...……………….3
1.3 The NHC’s Application in the Organometallic Chemistry and Catalysis……..5
1.4 Mirozoki-Heck Reaction……………….………………...………………........7
1.5 Transition-Metal NHC’s Application in Heck Coupling Reaction………........8
1.6 Copper Catalyzed B2(pin)2 Addition to Alkyne……………..………...………9
1.7 Transition-Metal NHC’s Application in Hydroboration of Alkyne……..……11
1.8 N-pyridyl Substituted NHC Stabilize Transition Metals…...………………...13
Chapter 2 Results and Discussion…...……………………………………….15
2.1 Preparation and Characterization of 4-Pyridyl-Substituted N-Heterocyclic
Carbenes…...………………………………………………………………….15
2.2 Preparation and Characterization of the 4-Picolyl-Linked N-Heterocyclic
Carbenes,………………………..…….............................................…...…....15
2.3 Preparation and Characterization of 4-Picolyl-NHC-AgCl2…...…………….18
2.4 Preparation and Characterization of 4-Picolyl-NHCmes-CuCl2 Complexes….23
2.5 Preparation and Characterization of 4-Picolyl-NHCi-pr-CuCl2 and4-Picolyl-NHCt-Bu-CuCl2 Complexes…………………………………………25
2.6 Preparation and Characterization of 4-Picolyl-NHCmes-NiCO3 Complexes…27
2.7 Preparation and Characterization of 4-Picolyl-NHCmes-PdCO3 Complexes…30
2.8 Preparation and Characterization of 4-Picolyl-NHCmes-PdCl2 Complexes…..32
2.9 Preparation and Characterization of 4-Picolyl-NHCi-pr-PdCl2 Complexes…..34
2.10 Preparation and Characterization of Phenyl-NHCi-pr-PdCl2 Complexes……..36
2.11 Palladium Complexes of NHC as Catalyst for the Mizoroki-Heck
Reaction……………………………………………………………………….38
2.12 Copper Complexes of NHC as Catalyst for the Hydroboration
of Alkyne……………………………..………………………..……………...46
Chapter 3 Experimental Section and Spectrum Data……………………..49
3.1 General Procedure……………………………………………………….…...49
3.2 Material and Methods……………………………………..………………….49
3.3 General Procedure for the Mizoroki-Heck Reaction…………………………50
3.4 General Procedure for Hydroboration…………………………………….….50
3.5 The Synthesis of Ligands and Metal Complexes…………………………….66
Chapter 4 Conclusion………………….……………………………….………67
Chapter 5 Reference……………...…………………………………….……….68
Appendix A: Single Crystal X-ray Characterization………………………..72
Appendix B: 1H and 13C NMR Spectrum……………………………………100

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指導教授

王朝諺、劉雅銘
(Tiow-Gan Ong、Ya-Ming Liu)

審核日期

2011-1-21

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