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http://hdl.handle.net/11455/16435| DC Field | Value | Language |
|---|---|---|
| dc.contributor | 葉鎮宇 | zh_TW |
| dc.contributor | 廖明淵 | zh_TW |
| dc.contributor.advisor | 陳如珍 | zh_TW |
| dc.contributor.author | 陳燕昭 | zh_TW |
| dc.contributor.author | Chen, Yen-Chao | en_US |
| dc.contributor.other | 中興大學 | zh_TW |
| dc.date | 2007 | zh_TW |
| dc.date.accessioned | 2014-06-06T06:55:25Z | - |
| dc.date.available | 2014-06-06T06:55:25Z | - |
| dc.identifier | U0005-0802200721495800 | zh_TW |
| dc.identifier.citation | 第一章 (1) Dickinson, R. E. In The Proteins; Neurath, H., Ed.; Academic Press: New York, 1964; Vol. 2, p 634. (2) Perutz, M.; Rossman, M. G.; Cullis, A. F.; Muirhead, H.; Will, G.; North, A. C. T. Nature 1960, 185, 416. (3) Takano, T.; Trus, B. L.; Mandel, N.; Mandel, G.; Kallai, O. B.; Swanson, R.; Dickerson, R. E. J. Biol. Chem. 1977, 252, 776-785. (4) Alexander, L. S.; Goff, H. M. J. Chem. Educ. 1982, 59, 179-182. (5) Scheidt, W. R.; Reed, C. A. Chem. Rev. 1981, 81, 543-555. (6) Goff, H.; La Mar, G. N.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 3641-3646. (7) Goff, H. M. Nuclear Magnetic Resonance of Iron Porphyrins. In Iron Porphyrin.; Lever, A. B. P.; Gray, H. B., Eds.; Physical Bioinorganic Chemistry series 1; Addison-Wesley: Reading, MA, 1983; pp 237 (8) Goff, H.; La Mar, G. N.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 3641 (9) Kurland, R. J.; McGarvey, B. R. J. Magn. Resonance. 1970, 2, 286. (10) Jesson, J. P. The Paramagnetic Shift. In NMR of Paramagnetic Molecules.; La Mar, G. N., Horrocks, W. D., Holm, R. H., Eds.; Academic Press: New York, 1973; pp 1-53 (11) McConnell, H. M. J. Chem. Phys. 1961, 35, 1312. (12) Walker, F. A. Proton NMR and EPR Spectroscopy of Paramagnetic Metalloporphyrins. In The Porphyrin Handbook.; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press:, 2000; Vol. 5, pp 165-299 (13) Goff, H.; La Mar, G. N.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 3641 (14) Karplus, M.; Fraenkel, G. K. J. Chem. Phy. 1961, 35, 1312. (15) La Mar, G. N.; Walker, F. A. Nuclear Magnetic Resonance of Paramagnetic. In The Porphyrins. 1st.; Dolphin, D., Eds.; Academic Press: New York, 1979; Vol. 4, pp 61-157 (16) La Mar, G. N. Biological Applications of Magnetic Resonance. In Biological Applications of Magnetic Resonance.; Shulman, R. G., Eds.; Academic Press: New York, 1979; pp 305-343 (17) Walker, F. A.; Simonis, U. Proton NMR Spectroscopy. In NMR of Paramagnetic Molecules.; Berliner, L. J., Reuben, J., Eds.; New York, 1993; Vol. 12, pp 133 (18) Shokhirev, N. V.; Walker, F. A. J. Phys. Chem. 1995, 99, 17795. (19) Gouterman, M. J. Chem. Phys. 1959, 30, 1139. (20) Zerner, M. C. Semiempirical Molecular Orbital Methods Ed.;Lipkowitz, K. B. and Boyd, D. B., Ed.;VCH Publishers: New York, 1991; Vol. 2, pp 313-365. (21) Zerner, M. C. Intermediate Neglect of Differential Overlap Calculations on the Electronic Spectra of Transition Metal ComplexesEd.;Russo, N. and Salahub, D. R., Ed.;Kluwer Academic Publishers: Netherlands, 1996; Vol. 2 , pp 493-531. (22) Edwards, W. D.; Diercksen, G. H. F.; Zerner, M. C. J. Mol. Struct. (Theochem). 1989, 199, 137-148. (23) Mispelter, J.; Momenteau, M.; Lhoste, J. M. J. Chem. Soc., Chem. Commun. 1979, 808-810. (24) 陳炳宇，中興大學化學系博士論文，2001. (25) Ghosh, A.; Gonzalez, E.; Vangberg, T. J. Phys. Chem. B. 1999, 103, 1363-1367. (26) Jentzen, W.; Simpson, M. C.; Hobbs, J. D.; Song, X.; Ema, T.; Nelson, N. Y.; Medforth, C. J.; Smith, K. 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Commun. 1995, 733. (36) Cheng, R.-J.; Chen, P.-Y.; Peng, S.-M. submitted. (37) Ghosh, A.; Gonzalez, E.; Vangberg, T. J. Phys. Chem. B. 1999, 103, 1363-1367. (38) Ru-Jen Cheng; Ping-Yu Chen; Pong-Ren Gau; Chun-Chia Chen; Shie-Ming Peng. J. Am. Chem. Soc. 1997, 119, 2563-2569. (39) Ru-Jen Cheng; Yen-Ku Wang; Ping-Yu Chen; Ya-Ping Han; Chih-Ching Chang. Chem. Commun. 2005, 1312–1314. (40) Nakamura, M.; Ikeue, T.; Fujii, H.; Yoshimura, T.; J. Am. Chem. Soc. 1997, 119, 6284-6291. (41) Ikeue, T.; Ohgo, Y.; Saitoh, T.; Yamaguchi, T.; Nakamura, M.; Inorg. Chem. 2001, 40, 3423-3434. (42) Ikezaki, A.; Nakamura, M.;Inorg. Chem. 2002, 41, 2761-2768. 第二章 (1) Rothemund, P. J. J. Am Chem. Soc. 1935, 57, 2010. (2) Rothemund, P. J.; Menotti, G. D. J. Am Chem. Soc. 1941, 63, 267. (3) Alder, A. D.; Sklar, L.; Longo, F. R. J. Heterocycl. Chem. 1968, 5, 669. (4) Sessler, J. L.; Mozaffari, A.; Johnson, M. R. Org. Synth. 1991, 70, 68. (5) Ono, M.; Lattmann, R.; Imomota, K.; Lehmann, C.; Fruh, T.; Eschenmoser, A. Croat. Chem.Acta 1985, 58, 627. (6) Schreiber, J.; Maag, H.; Hashimoto, N.; Eschenmoser, A. Angew, Chem. Int. Ed. Engl. 1971, 10, 330. (7) Whitlock, H. W.; Hanauer, R. J. J. Org. Chem. 1968, 33, 2169. (8) Eisner, U.; Lichtarowicz, A.; Linstead, R. P. J. Chem. Soc. 1957, 733. (9) Inhoffen, H. H.; Fuhrhop, J. H.; Voigt, H.; Brockmann, J. R. F. Ann. Chem. 1966, 695, 183. (10) Siedel, W.; Winkler, F. F. Ann. Chem. 1943, 554, 162. (11) Barton, D. H. R.; Zard, S. Z. J. Chem. Soc., Chem. Commun. 1985, 1098. (12) Barton, D. H. R.; Kervagoret, J.; Zard, S. Z. Tetrahedron 1990, 46, 7483. (13) Ono, N.; Kawamura, H.; Bougauchi, M.; Maruyama, K. Tetrahedron. 1990, 46. (14) Aoyagi, K.; Haga, T.; Toi, H.; Aoyama, Y.; Mizutani, T.; Ogoshi, H. Bull. Chem. Soc. Jpn 1997, 70, 937. (15) Dolphin, D. J. Heterocyclic Chem. 1970, 7, 275. (16) Evens, B.; Smith, K. M.; Fuhrhop, J. H. Tetrahedron Lett. 1977, 443. (17) Lindsey, J.; Wagner, R. J. Org. Chem. 1987, 52, 827-836. (18) Alder, A. D.; Longo, F. R.; Finarelli, J. D.; Goldmacher, J.; Assour, J.; Korsakoff, L. J. Org. Chem. 1967, 32, 476. (19) Dolphin, D.; Rousseau, K. Tetrahedron. Letters. 1974, 4251-4254. (20) Smith, K. M.; Barnett, G. H.; Hudson, M. F. J. Chem. Soc. Perkin I 1975, 1401-1403. (21) Jentzen, W.; Simpson, M. C.; Hobbs, J. D.; Song, X.; Ema, T.; Nelson, N. Y.; Medgorth, C. J.; Smith, K. M. J. Am. Chem. Soc. 1995, 117, 11085. (22) Ema, T.; Senge, M. O.; Nelson, N. Y.; Ogoshi, H.; Smith, K. M. Angew. Chem. Int. Ed. Engl. 1994, 33, 1879. (23) Neya, S.; Yodo, H.; Funasaki, N. J. Heterocyclic Chem. 1993, 30, 549. (24) Neya, S.; Funasaki, N. J. Heterocyclic Chem. 1997, 34, 689. (25) Hartman, G. D.; Weinstock, L. M. In Organic Synthesis, 620 (26) Ono, N. Bull. Chem. Soc. Jpn 1988, 61, 4470-4472. (27) Ferrand, J. C.; Schneider, R.; Gerardin, P.; Loubinoux, B. Synthetic communications. 1996, 26, 4329-4336. (28) Lightner, D. A.; Xie, M. Tetrahedron. 1994, 50, 8579-8596. (29) Lightner, D. A.; Nogales, D. F.; Anstine, D. T. Tetrahedron. 1993, 49, 2185-2200. (30) Lightner, D. A.; Byun, Y. S. J. Org. Chem. 1991, 56, 6027-6033. (31) Lindsey, J. S.; C., S. I.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52, 827-836. (32) Cheng, D. O.; Bowman, T. L.; LeGoff, E. Heterocyclic Chem. 1976, 13, 1145-1146. (33) Evans. J. Chem. Soc. ; 1959, 2005. 第三章 (1) Harold Goff and Gerd N. La Mar J. Am Chem. Soc. 1977, 99, 6599 (2) Nakamura, M. ; Fujii, H. J. Am Chem. Soc. 1997, 119, 6284 (3) Nakamura, M. Inorg. Chem. 2001, 40, 3423 (4) 國立中興大學化學系—王彥固 碩士論文 ”大環變形對五、六配位高自旋三價鐵卟啉對稱與鍵結的影響” 2004年7月 (5) Christopher A. Reed, Toshio Mashiko, W. Robert Scheidt, K. S~artaliana,n~d George Lang J. Am Chem. Soc. 1980, 102, 2302 第四章 (1) Nakamura, M. ; Fujii, H. J. Am Chem. Soc. 1997, 119, 6284 (2) Nakamura, M. Inorg. Chem. 2001, 40, 3423 (3) 國立中興大學化學系—王彥固 碩士論文 ”大環變形對五、六配位高自旋三價鐵卟啉對稱與鍵結的影響” 2004年7月 (4) Harold Goff and Gerd N. La Mar J. Am Chem. Soc. 1977, 99, 6599 (5) Mispelter, J. Biological Magnetic Resonance volume 12 NMR of Paramagnetic Molecules 1993, Chapter 6, 299 (6) Peter Turner Inorg. Chem. 1994, 33, 1406 (7) Karplus, M ; Fraenkel, G. K. J. Chem. Phy. 1961, 35, 1312 | zh_TW |
| dc.identifier.uri | http://hdl.handle.net/11455/16435 | - |
| dc.description.abstract | 越來越多的證據顯示非平面鐵卟啉普遍存在各種血紅素蛋白(hemoproteins)中，為了深入了解卟啉大環變形對其生物功能的影響，必須從相關非平面金屬卟啉模型化合物著手，全面探討其配位化學。已知大環變形會改變金屬卟啉的光電性質，尤其是透過降低對稱，增加金屬與卟啉的鍵結機會，進而影響其電子組態。 近年來，我們透過順磁金屬卟啉之1H、13C核磁共振光譜的測量，結合ADF理論計算和鍵結分析，發展出一套有效的方法，可深入探討金屬卟啉複雜的電子組態。針對四配位二價鐵卟啉(FeP)的研究顯示，大環變形並未明顯改變四配位二價鐵卟啉的中自旋電子組態。至於六配位三價鐵卟啉([FeIIIP(THF)2]+)，在平面TPP系統呈現高自旋電子組態(S = 5/2)，在馬鞍型和皺摺型系統卻呈現中自旋的(S = 3/2)性質，不過兩種變形會導致兩種不同中自旋電子組態。在皺摺型變形環境下，雖有dxy與a2u的鍵結作用，但其電子組態仍以(dxy)2 (dxz，yz)2 (dz2) 1為主；馬鞍型變形系統中，dxy與a1u的作用比在皺摺型變形環境下更強，呈現不尋常中自旋(dxz，yz)3(dxy)1(dz2) 1為主的電子組態。 已知平面型六配位二價鐵卟啉[FeII(TPP)(THF)2]為高自旋電子組態(S = 2)。從配位化學的觀點，THF為較弱的σ-donor，屬弱場配位基，較有機會呈現因大環變形所導致自旋狀態的改變。本篇論文即針對三個具有不同平面性之六配位二價鐵卟啉系統[FeII (TPP)(THF)2]、[FeII(OETPP)(THF)2]和[FeII(TiPP)(THF)2]，結合1H、13C核磁共振光譜分析以及ADF理論計算和鍵結分析等方法，詳細研究大環變形對二價鐵卟啉電子組態的影響。結果顯示大環變形確實引進新的鍵結作用，導致電子組態呈現不尋常的熱平衡現象。 綜合相關NMR的數據分析，[FeII (TPP)(THF)2]、[FeII(OMTPP)(THF)2]為單一的電子組態；[FeII(OETPP)(THF)2]、[FeII(TiPP)(THF)2]都不符合單一高自旋電子組態，而有中自旋或低自旋電子組態的貢獻。 比對理論計算，顯示Fe(TPP)(THF)2的NMR光譜的確符合高自旋電子組態，然而是屬於不尋常的高自旋5E (dxz、dyz)3(dxy)1 (dz2)1，不幸的是在相關的鍵結分析中並未發現影響dxz,yz軌域能量下降因素。 卟啉大環的變形降低六配位二價鐵卟啉對稱，增加鐵與大環的鍵結機會，此外可明顯觀察到大環變形改變六配位二價鐵卟啉之電子組態。平面的高自旋電子組態，因變形而形成中自旋的電子組態，亦再次印證大環變形對電子組態有影響。 | zh_TW |
| dc.description.tableofcontents | 一、背景介紹 (一) 關於血紅素蛋白-----------------------------------------------------------------1 (二) 金屬卟啉的基本介紹-----------------------------------------------------------7 (三) 順磁核磁共振光譜與金屬卟啉的電子組態--------------------------------9 (四) 理論計算-------------------------------------------------------------------------18 (五) 大環變形對電子組態與鍵結的影響----------------------------------------21 References---------------------------------------------------------------------------------31 二、金屬卟啉的合成及六配位四氫呋喃鐵卟啉錯合物的製備 (一) 緒論-------------------------------------------------------------------------------34 (二) 儀器設備-------------------------------------------------------------------------36 (三) 使用藥品-------------------------------------------------------------------------37 (四) Fe(P)Cl系列錯化物的合成---------------------------------------------------39 (五) 六配位四氫呋喃二價鐵卟啉錯合物的合成系列錯化物的合成-------54 ※ Evans’ Method-------------------- ----------------------------------------------55 ※ Zn/Hg (zinc amalgam)合成方法----------------------------------------------57 References---------------------------------------------------------------------------------58 三、六配位四氫呋喃二價鐵卟啉錯合物之鍵結特性 (一) 背景介紹-------------------------------------------------------------------------61 (二) 核磁共振光譜之分析---------------------------------------------------------63 1. Fe(TPP)(THF)2之鑑定與分析---------------------------------------------63 2. Fe(OETPP)(THF)2之鑑定與分析之鑑定與分析-----------------------67 3. Fe(OMTPP)(THF)2-----------------------------------------------------------71 4. Fe(TiPP)(THF)2之鑑定與分析---------------------------------------------76 5. 磁性測量----------------------------------------------------------------------83 References---------------------------------------------------------------------------------84 四、以理論計算探討六配位四氫呋喃二價鐵卟啉系列錯化物的電子組態與鍵結特性 (一) 背景介紹-------------------------------------------------------------------------85 (二) ADF計算數據------------------------------------------------------------------87 1. 計算方法--------------------------------------------------------------------87 2. 分子之幾何優選-----------------------------------------------------------88 3. 幾何優選之結果-----------------------------------------------------------89 4. 電子密度的分佈-----------------------------------------------------------95 5. 順磁核磁共振光譜之分析-----------------------------------------------98 6. Fragment計算-------------------------------------------------------------107 7. 鍵結分析-------------------------------------------------------------------107 (三) 結論----------------------------------------------------------------------------- 120 References--------------------------------------------------------------------------------121 五、結論--------------------------------------------------------------------------------------122 | zh_TW |
| dc.language.iso | en_US | zh_TW |
| dc.publisher | 化學系所 | zh_TW |
| dc.subject | porphyrin | en_US |
| dc.subject | 卟啉 | zh_TW |
| dc.title | 大環變形對六配位二價鐵卟啉 電子組態的影響 | zh_TW |
| dc.title | Influence on the Electron Configuration by Ring Deformation of Iron(II) Porphyrins | en_US |
| dc.type | Thesis and Dissertation | zh_TW |
| item.openairetype | Thesis and Dissertation | - |
| item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
| item.languageiso639-1 | en_US | - |
| item.grantfulltext | none | - |
| item.fulltext | no fulltext | - |
| item.cerifentitytype | Publications | - |
| Appears in Collections: | 化學系所 | |
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