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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯(Ching-Wen Chiu) | |
| dc.contributor.author | Bo-Jiun Chen | en |
| dc.contributor.author | 陳柏鈞 | zh_TW |
| dc.date.accessioned | 2021-07-11T14:37:49Z | - |
| dc.date.available | 2022-08-31 | |
| dc.date.copyright | 2017-08-31 | |
| dc.date.issued | 2017 | |
| dc.date.submitted | 2017-08-03 | |
| dc.identifier.citation | 1. Muetterties, E. L., J. Am. Chem. Soc. 1959, 81, 2597-2597.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77937 | - |
| dc.description.abstract | 為了要達成更高的路易士酸性，我們利用碳烯及吡啶組成的雙牙配基來穩定硼陽離子，並且由核磁共振與單晶鑑定；可惜，後續拔除氯離子的反應並不順利，無法如預期得到雙牙配基所穩定的兩價硼陽離子。另外，我們意外的發現吡啶碳烯與硼陽離子會進行氧化還原反應；根據理論計算，硼陽離子被碳烯還原後，會脫去一個氯離子，形成一個帶正電的自由基。此外，本研究也發現由低價數磷所組成的配基，並不適合用來配位硼化合物；Phospha-Wittig中的磷-磷鍵以及碳烯穩定的磷烯中的磷-碳鍵，在遇到硼烷後都會斷裂，至於二磷烯則因為立體障礙過大，而無法在磷上接上硼烷。 | zh_TW |
| dc.description.abstract | To achieve higher Lewis acidity of the boron species, a bidentate pyridyl-carbene stabilized boron cation is synthesized and characterized by NMR and X-ray crystallography. Unfortunately, the following chloride abstraction did not resulted in the targeted dicationic compound. Interestingly, an unexpected redox reaction of the boron cation and carbene was discovered during the synthesis of boronium. As indicated by theoretical calculations, the boronium would be reduced by carbene to yield a neutral radical, which then dissociates a chloride anion to form a radical cation. On the other hand, this study also revealed that the low-valent phosphorous-based ligands are proven to be not suitable towards Lewis acidic boranes. The P-P bond in phospha-Wittig and the P-C bond in NHC-stabilized phosphinidene readily break when treated with boranes, whereas diphosphene remained unreacted due to steric congestion at phosphorous center. | en |
| dc.description.provenance | Made available in DSpace on 2021-07-11T14:37:49Z (GMT). No. of bitstreams: 1 ntu-106-R04223128-1.pdf: 4303794 bytes, checksum: 658911951c100a5fa5806cf05060606d (MD5) Previous issue date: 2017 | en |
| dc.description.tableofcontents | 誌謝 i
中文摘要 ii ABSTRACT iii CONTENTS iv LIST OF FIGURES vi LIST OF SCHEMES vii LIST OF TABLE ix Chapter 1 Introduction 1 1.1 Lewis Acidic Boranes and Boron Cations 2 1.1.1 Boranes and Frustrated Lewis Pairs 2 1.1.2 Boron Monocations 4 1.1.3 Boron Dications 7 1.2 Di-substituted Boron Dications 9 1.2.1 NHC-Coordinated Boron Dication 9 1.2.2 NHO-Coordinated Boron Dication 11 1.2.3 CAAC-Coordinated Boron Dication 12 1.3 Electron Deficiency and Lewis Acidity 15 1.3.1 Experimental Evaluation 15 1.3.2 Theoretical Calculation 16 1.4 Phosphorous-Based Ligands 17 1.4.1 Phosphine-Coordinated Boron Cations 17 1.4.2 Phospha-Wittig 18 1.4.3 Carbene-Stabilized Phosphinidenes 20 1.4.4 Diphosphenes 21 1.5 Research Objective 22 1.5.1 Brief Summary 22 1.5.2 Molecular Design 22 Chapter 2 Results and Discussion 24 2.1 Starting Materials 24 2.2 Syntheses and Characterization 27 2.2.1 Pyridylcarbene-Stabilized Boronium 27 2.2.2 Phospha-Wittig and Dichlorophenylborane 31 2.2.3 NHC-Stabilized Phosphinidene and Borane 32 2.2.4 Diphosphene and Boranes 33 2.3 Radical Study 35 2.3.1 EPR and UV-Vis Spectra 35 2.3.2 Cyclic Voltammetry 37 2.3.3 Theoretical Calculation 38 Chapter 3 Conclusions 40 Chapter 4 Experimental Sections 41 References 52 Appendix 57 | |
| dc.language.iso | en | |
| dc.subject | 磷威剃 | zh_TW |
| dc.subject | 二磷烯 | zh_TW |
| dc.subject | 磷烯 | zh_TW |
| dc.subject | 自由基 | zh_TW |
| dc.subject | 硼陽離子 | zh_TW |
| dc.subject | 硼 | zh_TW |
| dc.subject | 路易士酸 | zh_TW |
| dc.subject | diphosphene | en |
| dc.subject | radicals | en |
| dc.subject | boron cations | en |
| dc.subject | phospha-Wittig | en |
| dc.subject | boron | en |
| dc.subject | phosphinidene | en |
| dc.title | 具十五族配位基之硼陽離子 | zh_TW |
| dc.title | Group 15 Ligands Coordinated Boron Cations | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 105-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 劉緒宗(Shiuh-Tzung Liu),林雅凡(Ya-Fan Lin) | |
| dc.subject.keyword | 路易士酸,硼,硼陽離子,自由基,磷威剃,磷烯,二磷烯, | zh_TW |
| dc.subject.keyword | boron,boron cations,radicals,phospha-Wittig,phosphinidene,diphosphene, | en |
| dc.relation.page | 110 | |
| dc.identifier.doi | 10.6342/NTU201702376 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2017-08-04 | |
| 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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