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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯(Ching-Wen Chiu) | |
| dc.contributor.author | Kuan-Yeh Lu | en |
| dc.contributor.author | 呂冠燁 | zh_TW |
| dc.date.accessioned | 2021-06-17T01:35:04Z | - |
| dc.date.available | 2020-08-29 | |
| dc.date.copyright | 2017-08-29 | |
| dc.date.issued | 2017 | |
| dc.date.submitted | 2017-08-02 | |
| dc.identifier.citation | 1. Yamaguchi, S.; Akiyama, S.; Tamao, K., J. Am. Chem. Soc. 2001, 123 (46), 11372-11375.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/67503 | - |
| dc.description.abstract | 在本論文中，1,2-雙(二苯基膦)乙烷配位之硼陽離子[1]+、(2-二苯基膦)吡啶配位之硼陽離子[3]+、(2-二叔丁基膦)吡啶配位之硼陽離子[4]+ 可被成功被合成，並利用核磁共振光譜鑑定。經由X-ray單晶繞射儀解析，[1]+為含雙膦基之五員環結構，而[3]+則是同時具有膦基及吡啶之高環張力四員環結構。與文獻報導過之十五族雙牙基配位所穩定之硼陽離子比較，[1]+ 與 [3]+ 具有較長的磷-硼鍵、更高的環張力，所以可以使其環形結構在遇到其他受質時更容易斷鍵，進而增強反應性。具有立體障礙更大的二叔丁基的 [4]+ 具有與 [3]+ 相似的11B NMR訊號，顯示 [4]+ 也具有相似的四員環結構。在反應性部分，[1][OTf] 可成功活化三乙基矽烷，產生膦-硼烷加合物1A，也可藉由受阻路易氏酸鹼對(frustrated Lewis pair)之反應機構來活化氫氣，顯示此類十五族雙牙基配位的環形硼陽離子比一般四配位硼陽離子具有更高反應性以及應用的潛力。 | zh_TW |
| dc.description.abstract | DPPE-coordinated boronium [1]+, Ph2P-Py-coordinated boronium [3]+, and tBu2P-Py-coordinated boronium [4]+ have been synthesized and characterized. The structure of [1]+ and [3]+ are confirmed by X-ray diffraction analysis. [1]+ shows a homoleptic five-membered ring, and [3]+ exhibits a highly-strained four-membered ring compared to reported bidendate group 15 ligands coordinated boroniums. Although having bulkier tBu2 group, [4]+ still presents cyclic structure similar to [3]+, which has been verified by 11B NMR spectrum. Reactivity study revealed that [1][OTf] can thermally activate Et3SiH through intramolecular frustrated Lewis pair mechanism to generate DPPE-9-BBN-H adduct (1A). It demonstrated that our cyclic boroniums bearing bidentate group 15 ligands have the potential to enhance the reactivity than usual tetra-coordinated boroniums. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-17T01:35:04Z (GMT). No. of bitstreams: 1 ntu-106-R04223104-1.pdf: 2275385 bytes, checksum: 00d0390da7409a656838ba95705ed50d (MD5) Previous issue date: 2017 | en |
| dc.description.tableofcontents | Abstract i 摘要 ii Contents iii List of Figures v List of Schemes vi List of Tables viii Chapter 1 Introduction 1 1.1 Boranes and Frustrated Lewis Pairs 1 1.2 Boron Cations 4 1.3 Research Objective 8 Chapter 2 Results and discussion 10 2.1 An overview 10 2.2 Syntheses and Characterizations of Boron Cations 11 2.2.1 With 9-BBN-H dimer 11 2.2.2 With 9-BBN-OTf 13 2.2.3 With 9-BBN-I 18 2.3 Reactivity Studies 22 2.3.1 Electrophilic Borylation 22 2.3.2 Hydrosilylation 24 2.3.3 Aromatic C-H Bond silylation 25 2.3.4 Hydrogenation 26 Chapter 3 Conclusion 27 Chapter 4 Experimental Section 29 Chapter 5 References 34 Chapter 6 Appendix 35 6.1 Crystal data 35 6.2 NMR spectra 52 | |
| dc.language.iso | en | |
| dc.subject | 硼陽離子 | zh_TW |
| dc.subject | boron cation | en |
| dc.subject | boronium | en |
| dc.title | 十五族雙牙基硼陽離子之合成與反應性探討 | zh_TW |
| dc.title | Syntheses and Reactivity Studies of Boron Cations Bearing Bidentate Group 15 Ligands | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 105-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 彭旭明(Shie-Ming Peng),林雅凡(Ya-Fan Lin) | |
| dc.subject.keyword | 硼陽離子, | zh_TW |
| dc.subject.keyword | boron cation,boronium, | en |
| dc.relation.page | 91 | |
| dc.identifier.doi | 10.6342/NTU201702440 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2017-08-02 | |
| 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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