Please use this identifier to cite or link to this item:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/60399Full metadata record
| ???org.dspace.app.webui.jsptag.ItemTag.dcfield??? | Value | Language |
|---|---|---|
| dc.contributor.advisor | 陳竹亭(Jwu-Ting Chen) | |
| dc.contributor.author | Jia-Jheng Lin | en |
| dc.contributor.author | 林佳正 | zh_TW |
| dc.date.accessioned | 2021-06-16T10:17:13Z | - |
| dc.date.available | 2015-09-02 | |
| dc.date.copyright | 2013-09-02 | |
| dc.date.issued | 2013 | |
| dc.date.submitted | 2013-08-17 | |
| dc.identifier.citation | 1. (a) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem. Int. Ed. Engl. 1999, 38, 428-447. (b) Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 1137-1138. (c) Togni, A.; Venanzi, L. M. Angew. Chem. Int. Ed. Engl. 1994, 33, 497-526. (d) Markies, B. A.; Verkerk, K. A. N.; Rietveld, M. H. P.; Boersma, J.; Kooijman, H.; Spek, A. L.; Vankoten, G. J. Chem. Soc. Chem. Commun. 1993, 1317-1319. (e) Schuster, G. B. Adv. Phys. Org. Chem. 1986, 22, 311-361.
2. (a) Togni, Antonio.; Venanzi, L. M. Angew. Chem. Int. Ed. Engl. 1994, 33, 497-526. (b) Fache, F.; Schulz, E.; Tommasino, M. L.; Lemaire, M. Chem. Rev. 2000, 100, 2159-2231. 3. (a) Lin, Y. -C., Ph.D. Thesis, “Investigation of Ethylene/Norbornene Copolymerization Using Cationic Methylpalladium(II) Catalysts with Amino-Pyridine Ligands”, National Taiwan University, Taipei, Taiwan, 2006. (b) Yu, K. -S., Ph.D. Thesis, “Heterotopic Bidentate Ligands and Their Roles in Catalysis-Mechanistic Approach to Reactions of Ethylene-Norbornene Copolymerization and Hydrogenation”, National Taiwan University, Taipei, Taiwan, 2012. 4. (a) Jolly, P. W. Angew. Chem. Int. Ed. Engl. 1985, 24, 283-295. (b) Mandal, S. K.; Gowda, G. A. N.; Krishnamurthy, S. S.; Nethaji, M. Dalton trans. 2003, 1016-1027. (c) Trost, B. M.; Vranken, D. L. V. Chem. Rev. 1996, 96, 395-422. 5. Wang, C. -C., Master Thesis, “Synthesis and Catalysis of Thioethers-Functionalized N-Heterocyclic Carbene Palladium Complexes”, National Taiwan University, Taipei, Taiwan, 2012. 6. (a) Takao, Y.; Takeda, T.; Watanabe, J.; Setsune, J. Organometallics 1999, 18, 2936-2938. (b) Torre, F. G. T.; Hoz, A.; Jalon, F. A.; Manzano, B. R.; Rodriguez, A. M.; Elguero, J.; Martinez-Ripoll, M. Inorg. Chem. 2000, 39, 1152-1162. (c) Carrion, M. C.; Diaz, A.; Guerrero, A.; Jalon, F. A.; Manzano, B. R.; Rodriguez, A.; Paul, R. L.; Jeffery, J. C. J. Organomet. Chem. 2002, 650, 210-222. (d) Albinati, A. R.; Kunz, W.; Ammann, C. J.; Pregosin, P. S. Organometallics 1991, 10, 1800-1806. 7. (a) Gogoll, A.; Grennberg, H.; Axen, A. Organometallics 1997, 16, 1167-1178. (b) Elguero, J.; ruchier, A.; Hoz, F. A.; Jalon, F. A.; Manzano, B. R.; Otero, A.; Torre, F. G. Chem. Ber. 1996, 129, 589-594. (c) Delis, J. G. P.; Groeen, J. H.; Vrieze, K.; Leeuwen, P. W. N. M.; Veldman, N.; Spek, A. L. Organometallics 1997, 16, 551-562. (d) Faller, J. W.; Stokes-Huby, H. L.; Albrizzio, M. A. Helv. Chim. Acta 2001, 84, 3031-3042. 8. (a) Crociani, B.; Bianca, F. D.; Giovenco, A.; Boschi, T. Inorg. Chim. Acta 1987, 127, 169-182. (b) Crociani, B.; Antonaroli, S.; Paci, M.; Bianca, F. D.; Canovese, L. Organometallics 1997, 16, 384-391. (c) Carrion, M. C.; Diaz, A.; Guerrero, A.; Jalon, F. A.; Manzano, B. R.; Rodriguez, A.; Paul, R. L.; Jeffery, J. C. J. Organomet. Chem. 2002, 650, 210-222. (d) Hansson, S.; Norrby, P-O.; Sjogren, M. P. T.; Akermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (e) Haaren, R. J.; Goubitz, K.; Fraanje, J.; Strijdonck, G. P. F. V.; Oevering, H.; Coussens, B.; Reek, J. N. H.; Kamer, P. C. J.; Leeuwen, P. W. N. M. Inorg. Chem. 2001, 40, 3363-3372. 9. Cucciolito, M.; Giordano, E. F.; Vitagliano, A.; Hansson, S.; Norrby, P-O.; Sjogren, M. P. T.; Akermar, B. Organometallics 1993, 12, 4940-4948. 10. Montoya, V.; Pons, J.; Garcia-Anton, J.; Solans, X.; Font-Bardia, M.; Ros, J. Organometallics 2007, 26, 3183-3190. 11. Crociani, B.; Antonaroli, S.; Paci, M.; Bianca, F. D.; Canovese, L. Organometallics 1997, 16, 384-391. 12. Yeh, C. -L., Master Thesis, “The Synthesis, Structures and Nucleophilic Addition Reaction of (α-Imino-Amino)(η3-Allyl)Palladium(II) Complexes”, National Taiwan University, Taipei, Taiwan, 2001. 13. Breutel, C.; Pregosin, P. S.; Salzmann, R.; Togni, A. J. Am. Chem. Soc. 1994, 116, 4067-4068. 14. (a) Adam, R. D.; Chodosh, D. F.; Faller, J. W.; Rosan, A. M. J. Am. Chem. Soc. 1979, 101, 2570-2575. (b) Faller, J. W.; Chao, K. -H. J. Am. Chem. Soc. 1983, 105, 3893-3898. (c) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 15231526. (d) Cho, C. -W.; Son, J. -H.; Ahn, K. H. Tetrahedron: Asym. 2006, 17, 2240-2241. 15. Mandal, S. K.; Gowda, G. A. N.; Krishnamurthy, S. S.; Zheng, C.; Li, S. -J.; Hosmane, N. S. J. Organomet. Chem. 2003, 676, 22-37. 16. Bichler, B.; Veiros, L. F.; Oztopcu, O.; Puchberger, M.; Mereiter, K.; Matsubara, K.; Kirchner, K. A. Organometallics 2011, 30, 5928-5942. 17. Jalon, F. A.; Manzano, B. R.; Moreno-Lara, B. Eur. J. Inorg. Chem. 2005, 1, 100-109. 18. Ficks, A.; Sibbald, C.; John, M.; Dechert, S.; Meyer, F. Organometallics 2010, 29, 1117-1126. 19. (a) Powell, J.; Robinson, S. D.; Shaw, B. L. Chem. Commun. 1965, 5, 78-79. (b) Kumar, P. G. A.; Dotta, P.; Hermatschweiler, R.; Pregosin, P. S.; Albinati, A.; Rizzato, S. Organometallics 2005, 24, 1306-1314. (c) Faller, J. W.; Wilt, J. C. Organometallics 2005, 24, 5076-5083. (d) Filipuzzi, S.; Pregosin, P. S.; Albinati, A.; Rizzato, S. Organometallics 2006, 25, 5955-5964. (e) Mikhael, I.; Goux-Henry, C.; Sinou, D. Tetrahedron Asym. 2006, 17, 1853-1858. (f) Wassenaar, J.; van Zutphen, S.; Mora, G.; Floch, P. L.; Siegler, M. A.; Spek, A. L.; Reek, J. N. H. Organometallics 2009, 28, 2724-2734. 20. (a) Pal, S. J. Chem. Sci. 2010, 122, 471-480. (b) Abergel, D.; Palmer, A. G. Chem. Phys. Chem. 2004, 5, 787-793. (c) Bain, A. D.; Cramer J. A. J. Phys. Chem. 1993, 97, 2884-2887. (d) Shokhirev, N. V.; Shokhireva, T. K.; Polam, J. R.; Watson, C. T.; Raffii, K.; Simonis, U.; Walker, F. A. J. Phys. Chem. A 1997, 101, 2778-2786. (e) Cronin, L.; Higgitt, C. L.; Perutz, R. N. Organometallics 2000, 19, 672-683. 21. (a) Gutowsky, H. S.; Holm, C. H. J. Chem. Phys. 1956, 25, 1228-1234. (b) Sandstro, J., Dynamic NMR Spectroscopy, Academic Press, New York, 1982. 22. (a) Bastero, A.; Ruiz, A.; Claver, C.; Milani, B.; Zangrando, E. Organometallics 2002, 21, 5820-5829. (b) Canovese, L.; Visentin, F.; Chessa, G.; Uguagliati, P.; Bandoli, G. Organometallics 2000, 19, 1461-1463. 23. (a) Moreno, A.; Pregosin, P. S. Organometallics 2009, 28, 6489-6506. (b) Barbara, P.; Paul S.; Pregosin, S. P.; Salzmann, S. Organometallics 1995, 14, 5160-5170. (c) Barbara, P.; Paul S.; Pregosin, S. P.; Salzmann, S. Organometallics 1995, 14, 5160-5170. (d) Mechria, A.; Rzaiguib, M.; Bouachira, F. Tetrahedron Letters 2000, 41, 719-7202. 24. (a) Nishimura, S., Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis, Wiley-VCH, Weinheim 2001. (b) de Vries, J. G.; Elsevier, C. J., Handbook of Homogeneous Hydrogenation, Wiley-VCH, Weinheim 2007. 25. (a) Widegren, J. A.; Bennett, M. A.; Finke, R. G. J. Am. Chem. Soc. 2003, 125, 10301-10310. (b) Hagen, C. M., Widegren, J. A.; Maitlis, P. M.; Finke, R. G. J. Am. Chem. Soc. 2005, 127, 4423-4432. 26. (a) Xie, J. -H.; Zhu, S. -F.; Zhou, Q. -L. Chem. Rev. 2011, 111, 1713-1760. (b) Wang, D. -S.; Chen, Q. -A.; Lu S. -M.; Zhou, Y. -G. Chem. Rev. 2012, 112, 2557-2590. (c) Dub, P. A.; Takao, I. ACS Catal. 2012, 2, 1718−1741. (d) Rode, C. V.; Vaidya, M. J.; Chaudhari, R. V. Organic Process Research & Development 1999, 3, 465-470. 27. (a) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; Lavalleye, J. P. P. M.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E. M. Organometallics 1985, 4, 1819-1830. (b) Widegren, J. A.; Bennett, M. A.; Finke, R. G. J. Am. Chem. Soc. 2003, 125, 10301-10310. (c) Hagen, C. M.; Widegren, J. A.; Maitlis, P. M.; Finke, R. G. J. Am. Chem. Soc. 2005, 127, 4423-4432. 28. Marion, N.; Navarro, O.; Mei, J.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. J. Am. Chem. Soc. 2006, 128, 4101-4111. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/60399 | - |
| dc.description.abstract | 本研究合成了一系列含α-胺基-吡啶雙牙配位基之烯丙基有機鈀錯合物 [Pd(η3-C3H4R3)(Pyridine-CHR1NHR2)](BF4) (R1 = 氫、甲基；R2 = 2,6-二異丙基苯基、2,6-二甲基苯基、苯基、三級丁基、異丙基；R3 = 氫、甲基、苯基)。產物運用二維核磁共振技術及X光結晶學加以鑑定。這些錯合物 (R1 = 氫) 具有含掌性中心的胺基以及有取代基的烯丙基，因此在核磁共振光譜中可以觀察到四種主要的非鏡像異構物，而各種異構物的比例主要是由胺基和烯丙基上的取代基的立體效應所主導。
在二維NOESY光譜中觀察到四種異構物，彼此會進行快速的異構化轉換。分子流變行為不僅發生在烯丙基部份，也同時發生胺基-吡啶雙牙配位基上，烯丙基基團旋轉以及胺基反轉的能量屏障則是進一步以選擇性NOESY光譜分析和變溫核磁共振實驗加以求得。另外，我們也嘗試將這些有機鈀錯合物應用在不飽和化合物的氫化反應上，並且觀察到不錯的反應活性，然而透過汞毒化、過濾實驗以及穿透式電子顯微鏡影像，顯示催化的活性物質是平均直徑為523奈米的金屬奈米粒子，這可能是由於胺基-吡啶雙牙配位基的弱α-予體能力無法保護零價的鈀物種，因而進一步聚集在一起。 | zh_TW |
| dc.description.abstract | A series of cationic allylpalladium(II) complexes with the α-amino-pyridine ligands in the formula of [Pd(η3-C3H4R3)(Pyridine-CHR1NHR2)](BF4) (R1 = H, Me; R2 = 2,6-iPr2C6H3, 2,6-Me2C6H3, Ph, tBu, iPr; R3 = H, Me, Ph) had been synthesized and characterized by 2D NMR and X-ray crystallographic techniques. These complexes (R1 = H) that contained chiral amino group and substituted allyl group afforded four major diastereomers in NMR spectra. The distribution of isomers might be primarily contributed from the steric effect of amino moiety and substituent on allyl group.
Rapid isomerization among the isomers was observed in 2D NOESY spectra. The fluxional behavior in solution took place in both allylic moiety and amino-pyridine ligands. The energy barriers of allyl pseudo-rotation and amine inversion were further determined by selective NOESY spectra analysis and variable-temperature NMR experiments. These organopalladium species were also applied to catalyze the hydrogenation of unsaturated substrates and showed comparable activity. However, the mercury poison, filtration experiments and TEM images revealed the active species was metal nanoparticles with average diameter 523 nm. These results might be arisen from the α-amino-pyridine ligands couldn't protect the Pd(0) species from aggregation because of weak σ-donating ability. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T10:17:13Z (GMT). No. of bitstreams: 1 ntu-102-R00223150-1.pdf: 8836889 bytes, checksum: e77a0d7f2f95a26d6a32a22726494335 (MD5) Previous issue date: 2013 | en |
| dc.description.tableofcontents | Chapter 1. Introduction of Allylpalladium Complexes with the N-donor Ligands (1)
1-1. Bidentate Nitrogen Ligands and Methylpalladium Complexes with the α-Amino-Pyridine Ligands(1) 1-2. The Dynamic Behavior in Solution of Allylpalladium Complexes (4) 1-3. Isomer distribution and Catalytic Application of Allylpalladium Complexes with the N-donor Ligands (8) 1-4. Goal of this Thesis (12) Chapter 2. Synthesis and Characterization of Allylpalladium Complexes with the α-Amino-Pyridine Ligands (13) 2-1. Synthesis of α-Amino-Pyridine Ligands (13) 2-2. Synthesis of Allylpalladium Complexes (15) 2-3. Characterization of Allylpalladium Complexes (16) 2-4. The Dynamic Behavior in Solution of the Allylpalladium Complexes and Selective NOESY Spectra Analysis (29)) 2-5. Variable-Temperature 1H NMR Spectroscopy Analysis of the Allylpalladium Complexes (47) 2-6. X-ray Single-Crystal Analysis (56) Chapter 3. Catalytic Applications of Allylpalladium Complexes with the α-Amino-Pyridine Ligands (64) 3-1. Introduction of Hydrogenation (64) 3-2. Hydrogenation Catalyzed by Allylpalladium Complexes (65) Chapter 4. Conclusion (72) Chapter 5. Experimental Section (74) 5-1. General Procedure (74) 5-2. Physical Measurement (74) 5-3. Synthesis and Spectral Characterization (75) 5-4. X-ray Crystallographic Analysis (125) 5-5. General Procedure for Selective NOESY Spectra Analysis (125) 5-6. General Procedure for VT-NMR Isomerization Kinetics (126) 5-7. General Procedure for Hydrogenation (127) 5-8. General Procedure for Transmission Electron Microscopy Analysis (127) References (128) Appendix (134) | |
| dc.language.iso | en | |
| dc.subject | 胺基-吡 | zh_TW |
| dc.subject | 鈀 | zh_TW |
| dc.subject | 啶 | zh_TW |
| dc.subject | 流變行為 | zh_TW |
| dc.subject | 氫化 | zh_TW |
| dc.subject | 烯丙基 | zh_TW |
| dc.subject | 異構化 | zh_TW |
| dc.subject | hydrogenation | en |
| dc.subject | amino-pyridine | en |
| dc.subject | allyl | en |
| dc.subject | isomerization | en |
| dc.subject | dynamic behavior | en |
| dc.subject | fluxional behavior | en |
| dc.subject | palladium | en |
| dc.title | 含α-胺基-吡啶雙牙配位基之烯丙基有機鈀錯合物之合成、
異構及催化 | zh_TW |
| dc.title | The Synthesis, Isomerization and Catalysis of Allylpalladium(II) Complexes with the α-Amino-Pyridine Ligands | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 101-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 劉緒宗(Shiuh-Tzung Liu),林英智(Ying-Chih Lin),許益瑞(I-Jui Hsu) | |
| dc.subject.keyword | 鈀,胺基-吡,啶,烯丙基,異構化,流變行為,氫化, | zh_TW |
| dc.subject.keyword | palladium,amino-pyridine,allyl,isomerization,dynamic behavior,fluxional behavior,hydrogenation, | en |
| dc.relation.page | 148 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2013-08-17 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| Appears in Collections: | 化學系 | |
Files in This Item:
| File | Size | Format | |
|---|---|---|---|
| ntu-102-1.pdf Restricted Access | 8.63 MB | Adobe PDF |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.