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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/81182完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯(Ching-Wen Chiu) | |
| dc.contributor.author | Po-Han Chen | en |
| dc.contributor.author | 陳柏翰 | zh_TW |
| dc.date.accessioned | 2022-11-24T03:34:49Z | - |
| dc.date.available | 2026-08-06 | |
| dc.date.available | 2022-11-24T03:34:49Z | - |
| dc.date.copyright | 2021-08-11 | |
| dc.date.issued | 2021 | |
| dc.date.submitted | 2021-08-06 | |
| dc.identifier.citation | 1. Shoji, Y.; Tanaka, N.; Mikami, K.; Uchiyama, M.; Fukushima, T., A two-coordinate boron cation featuring C–B+–C bonding. Nat. Chem. 2014, 6 (6), 498-503. 2. Tseng, H.-C.; Shen, C.-T.; Matsumoto, K.; Shih, D.-N.; Liu, Y.-H.; Peng, S.-M.; Yamaguchi, S.; Lin, Y.-F.; Chiu, C.-W., [η5-Cp*B-Mes]+: A masked potent boron lewis acid. Organometallics 2019, 38 (22), 4516-4521. 3. Burkhardt, E. R.; Matos, K., Boron reagents in process chemistry: Excellent tools for selective reductions. Chem. Rev. 2006, 106 (7), 2617-2650. 4. Eisenberger, P.; Crudden, C. M., Borocation catalysis. Dalton Trans. 2017, 46 (15), 4874-4887. 5. Reus, C.; Wagner, M., Boron served straight up. Nat. Chem. 2014, 6 (6), 466-467. 6. Shoji, Y.; Tanaka, N.; Hashizume, D.; Fukushima, T., The molecular and electronic structures of a thioaroyl cation formed by borinium ion-mediated C=S double bond cleavage of CS2. Chem. Commun. 2015, 51 (69), 13342-13345. 7. Tanaka, N.; Shoji, Y.; Hashizume, D.; Sugimoto, M.; Fukushima, T., Formation of an isolable divinylborinium ion through twofold 1,2-carboboration between a diarylborinium ion and diphenylacetylene. Angew. Chem. Int. Ed. 2017, 56 (19), 5312-5316. 8. Bamford, K. L.; Qu, Z.-W.; Stephan, D. W., Activation of H2 and Et3SiH by the borinium cation [Mes2B]+: Avenues to cations [MesB(μ-H)2(μ-Mes)BMes]+ and [H2B(μ-H)(μ-Mes)B(μ-Mes)(μ-H)BH2]+. J. Am. Chem. Soc. 2019, 141 (15), 6180-6184. 9. Higashi, J.; Eastman, A. D.; Parry, R. W., Synthesis and characterization of salts of the bis(diisopropylamido)boron(III) cation and attempted reactions to make the corresponding bis(dimethylamido)boron(III) cation. Inorg. Chem. 1982, 21 (2), 716-720. 10. Major, C. J.; Bamford, K. L.; Qu, Z.-W.; Stephan, D. W., Hydroboration without a B–H bond: reactions of the borinium cation [(iPr2N)2B]+ with alkyne, nitrile, ketone and diazomethane. Chem. Commun. 2019, 55 (35), 5155-5158. 11. Brown, H. C.; Zweifel, G., A stereospecific cis hydration of the double bond in cyclic derivatives. J. Am. Chem. Soc. 1959, 81 (1), 247-247. 12. Yamaguchi, S.; Akiyama, S.; Tamao, K., Colorimetric fluoride ion sensing by boron-containing π-electron systems. J. Am. Chem. Soc. 2001, 123 (46), 11372-11375. 13. Braunschweig, H.; Kupfer, T., Recent developments in the chemistry of antiaromatic boroles. Chem. Commun. 2011, 47 (39), 10903-10914. 14. Jiang, C.; Blacque, O.; Berke, H., Activation of terminal alkynes by frustrated lewis pairs. Organometallics 2010, 29 (1), 125-133. 15. Möbus, J.; Bonnin, Q.; Ueda, K.; Fröhlich, R.; Itami, K.; Kehr, G.; Erker, G., The 1,1-carboboration of bis(alkynyl)phosphanes as a route to phosphole compounds. Angew. Chem. Int. Ed. 2012, 51 (8), 1954-1957. 16. Piers, W. E.; Bourke, S. C.; Conroy, K. D., Borinium, borenium, and boronium ions: Synthesis, reactivity, and applications. Angew. Chem. Int. Ed. 2005, 44 (32), 5016-5036. 17. Prokofjevs, A.; Kampf, J. W.; Vedejs, E., A boronium ion with exceptional electrophilicity. Angew. Chem. Int. Ed. 2011, 50 (9), 2098-2101. 18. Farrell, J. M.; Hatnean, J. A.; Stephan, D. W., Activation of hydrogen and hydrogenation catalysis by a borenium cation. J. Am. Chem. Soc. 2012, 134 (38), 15728-15731. 19. Noeth, H.; Staudigl, R.; Wagner, H. U., Contributions to the chemistry of boron. 121. dicoordinate amidoboron cations. Inorg. Chem. 1982, 21 (2), 706-716. 20. Courtenay, S.; Mutus, J. Y.; Schurko, R. W.; Stephan, D. W., The extended borinium cation: [(tBu3PN)2B]+. Angew. Chem. Int. Ed. 2002, 41 (3), 498-501. 21. Möhlen, M.; Neumüller, B.; Faza, N.; Müller, C.; Massa, W.; Dehnicke, K., Phosphaniminato-komplexe von bor. synthese und kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2. Z. Anorg. Allg. Chem. 1997, 623 (10), 1567-1576. 22. Möhlen, M.; Neumüller, B.; Harms, K.; Krautscheid, H.; Fenske, D.; Diedenhofen, M.; Frenking, G.; Dehnicke, K., Tri(phosphorano)borazinium-ionen. Z. Anorg. Allg. Chem. 1998, 624 (7), 1105-1110. 23. Möhlen, M.; Neumüller, B.; Dehnicke, K., [(HBNPEt3)4NPEt3]3+ – ein bicyclisches penta(phosphorano)boraziniumtrikation. Z. Anorg. Allg. Chem. 1999, 625 (2), 197-199. 24. Davidson, J. M.; French, C. M., 23. The existence of an organic cation containing boron. J. Am. Chem. Soc. 1958, (0), 114-117. 25. Nöth, H.; Staudig, R., Boron cations with a dicoordinate B atom. Angew. Chem. Int. Ed. 1981, 20 (9), 794-795. 26. Franz, D.; Szilvási, T.; Pöthig, A.; Inoue, S., Isolation of an N-heterocyclic carbene complex of a borasilene. Chem. Eur. J. 2019, 25 (47), 11036-11041. 27. Bamford, K. L.; Stephan, D. W., Insertion reactions of the C–B–N-substituted borinium cation [MesBNiPr2]+. Dalton Trans. 2020, 49 (48), 17571-17577. 28. Ooi, T.; Miura, T.; Ohmatsu, K.; Saito, A.; Maruoka, K., Meerwein–Ponndorf–Verley alkynylation of aldehydes: Essential modification of aluminium alkoxides for rate acceleration and asymmetric synthesis. Org. Biomol. Chem. 2004, 2 (22), 3312-3319. 29. Fujimoto, K.; Yorimitsu, H.; Osuka, A., Porphyrinylboranes synthesized via porphyrinyllithiums. Chem. Eur. J. 2015, 21 (32), 11311-11314. 30. Blackwell, J. M.; Sonmor, E. R.; Scoccitti, T.; Piers, W. E., B(C6F5)3-catalyzed hydrosilation of imines via silyliminium intermediates. Org. Lett. 2000, 2 (24), 3921-3923. 31. Lambert, J. B.; Zhang, S.; Stern, C. L.; Huffman, J. C., Crystal structure of a silyl cation with no coordination to anion and distant coordination to solvent. Science 1993, 260 (5116), 1917-8. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/81182 | - |
| dc.description.abstract | 硼陽離子是一種高度缺乏電子的線性雙配位硼陽離子，一般都需要兩個具有-推電子性質之氨基來穩定，反應性研究也相對少。近期研究報導指出二芳基苯雙配位硼陽離子（[Mes2B]+）可與二氧化碳、氫氣、二苯乙炔、矽烷等反應，且反應模式與較穩定的三配位硼陽離子不同，所以在過去幾年中受到了相當多的關注。然而，在所有報導的二芳基雙配位硼陽離子的反應中觀察到，所有反應皆與芳基-硼鍵的斷裂相關，顯示此類化合物並不具有潛在的催化應用。為了探究如何可以讓雙配位硼陽離子可以具有催化應用，我們決定研究芳基氨基取代之雙配位硼陽離子[Ar-B+-NR2]的合成，並探討此類化合物的催化潛力。在本論文中，我們成功合成了一個穩定的、具有C–B–N結構的二配位硼陽離子[Mes-B-TMP] [B(C6F5)4]，並將其應用於酮和醛的矽氫加成、矽氰加成、以及硼氫加成反應上。 初步結果表明，羰基與硼陽離子的配位反應會降低硼陽離子的催化活性，顯示催化反應的活化步驟不涉及羰基對硼陽離子的配位。 | zh_TW |
| dc.description.provenance | Made available in DSpace on 2022-11-24T03:34:49Z (GMT). No. of bitstreams: 1 U0001-0308202114572300.pdf: 14894674 bytes, checksum: 501740f8f862baacd138d697e2bf9f3c (MD5) Previous issue date: 2021 | en |
| dc.description.tableofcontents | "口試委員會審定書 ---------------i 謝誌 ----------------------ii 摘要 ---------------------iii Abstract --------------iv Contents ---------------v List of Figures ------------viii List of Schemes -------------xii List of Tables --------------------xiii Chapter 1. Introduction --------1 1.1 Boranes ------------2 1.2 Boron Mono Cations -----------5 1.3 Research Objective -----------12 Chapter 2. Results and Discussions ----------14 2.1 Syntheses and Characterization ------14 2.1.1 Mes-B+-TMP Borinium ion ----------14 2.1.1.1 Acidity Measurement ---------18 2.1.1.2 Cyanosilylation of ketone and aldehyde ----------20 2.1.1.3 hydrosilylation of ketone and aldehyde ---------25 2.1.2 Mes-B+-HMDS Borinium ion ----------29 2.1.3 Mes-B+-Carbozole Borinium ion --------35 2.1.4 Other C-B-N substituted Borinium ion ----------37 Chapter 3. Conclusion ---------38 Chapter 4. Experimental Section -----------39 General experimental information: ----------39 Preparation of MesBCl2 ---------40 Preparation of Na[B(C6F5)4], Na[BArF] --------41 Preparation of K[B(C6F5)4], K[BArF] ---------42 Preparation of [Ph3C][B(C6F5)4], Trityl [BArF] ---------43 Preparation of [SiEt3][B(C6F5)4], [Et3Si][BArF] --------43 Preparation of TMPLi ---------44 Preparation of CarbazoleLi ---------44 Preparation of MesB(Cl)TMP, 1 ----------45 Preparation of [MesBTMP][Al(OC(CF3)3)4], [2][Al(OC(CF3)3)4] --------46 Preparation of MesB(CN)TMP, 5 ------46 Preparation of [Mes(TMP)BCNBMes(TMP)][Al(OC(CF3)3)4], [6][Al(OC(CF3)3)4]--------47 Preparation of MesB(Cl)HMDS, 10---------48 Preparation of [MesB(CH3)N(Si(CH3)2)TMS][Al(OC(CF3)3)4], [11][Al(OC(CF3)3)4]-------49 Preparation of MesB(CH3)N(SiCl(CH3)2)TMS, 12 -------49 Preparation of MesB(Cl)Carbazole, 13 -----50 Preparation of 2,4,6-triisopropylphenylcopper, TripCu -------51 Preparation of dichloro(2,4,6-triisopropylphenyl)borane, TripBCl2 ----51 [2][Al(OC(CF3)3)4] reacts with Et3PO --------52 Reaction of acetophenone with [2][Al(OC(CF3)3)4] -------52 Reaction of TMSCN with [2][Al(OC(CF3)3)4] --------53 Reaction of Et3SiH with [2][Al(OC(CF3)3)4] --------53 [TMSCNTMS][BArF] comes from [Mes2B][BArF] reacting with TMSCN. ------54 Catalytic cyanosilylation of Ketones and Aldehydes by [2]+ ------54 Catalytic cyanosilylation of 3a by [TMSCN-TMS]+ or [6]+ ---56 Catalytic hydrosilylation/deoxygenation of Ketones and Aldehydes by [2]+--------57 Catalytic deoxygenation of 8a by [2]+ ----59 References ------60 Chapter 5. Supporting Information -------63 5.1 Appendix -------63 5.1.1 Crystal Data ---------63 5.1.1 Crystal data for 1 ------63 5.1.2 Crystal data for 5 --------69 5.1.3 Crystal data for [6][Al(OC(CF3)3)4] --75 5.1.4 Crystal data for 10 ----92 5.1.5 Crystal data for [11][Al(OC(CF3)3)4] --99 5.1.6 Crystal data for 13 -------117 5.1.7 Crystal data for [TMSCNTMS][BArF] -------129 5.1.2 Estimation of Lewis Acidity----------141 5.1.2.1 Estimation of Lewis acidity of [2][Al(OC(CF3)3)4]-------141 5.1.2.2 Competition experiment of [2][Al(OC(CF3)3)4] and B(C6F5)3-----141 5.1.3 Catalytic hydrosilylation/deoxygenation of ketone 3a by [Et3Si][BArF]------143 5.1.4 NMR Spectrum----------144 " | |
| dc.language.iso | en | |
| dc.subject | 路易斯酸 | zh_TW |
| dc.subject | 低配位 | zh_TW |
| dc.subject | 催化反應 | zh_TW |
| dc.subject | 硼陽離子 | zh_TW |
| dc.subject | 硼化物 | zh_TW |
| dc.subject | Boron cation | en |
| dc.subject | catalytic reaction | en |
| dc.subject | low coordination | en |
| dc.subject | borinium | en |
| dc.subject | Lewis acid | en |
| dc.subject | boron compound | en |
| dc.title | [C-B+-N]硼陽離子之合成與催化反應探討 | zh_TW |
| dc.title | Aryl Amino Borinium Cations: Synthesis and Catalysis | en |
| dc.date.schoolyear | 109-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 王華冬(Hsin-Tsai Liu),陳喧應(Chih-Yang Tseng),蔡蘊明 | |
| dc.subject.keyword | 硼陽離子,催化反應,低配位,路易斯酸,硼化物, | zh_TW |
| dc.subject.keyword | Boron cation,catalytic reaction,low coordination,borinium,Lewis acid,boron compound, | en |
| dc.relation.page | 229 | |
| dc.identifier.doi | 10.6342/NTU202102043 | |
| dc.rights.note | 同意授權(限校園內公開) | |
| dc.date.accepted | 2021-08-06 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| dc.date.embargo-lift | 2026-08-06 | - |
| 顯示於系所單位： | 化學系 | |
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