臺灣博碩士論文加值系統

本論文採用金屬模板效應的方法合成十四圓環1.4.8.11-tetraazacyclotetradecane (cyclam)，再於氮上接一單取代基形成1-(2-Pyridylmethyl)-1.4.8.11-tetraazacyclotetradecane，此化合物可與鎳(II)金屬形成六配位的金屬錯合物，其中一個配位乃是水分子鍵結於軸位上所造成。
本文中，將[Ni (cyclam-CH2-Py)(H2O)]2+與各種單牙配位基進行軸位取代反應，根據Rose-Drago方程式可求得其平衡常數的大小依序為：N3- > SCN- > Cl- > Br-，顯示出其平衡常數會隨著單牙配位基鹼度的增加而加大，與取代基的軟度較無關係。再將陰離子取代基的軟度及鹼度等因素代入Edwards方程式，並與過去的文獻作比較，可知本實驗鎳(II)金屬錯合物的軟硬度是屬於boarder line的性質。
再根據動力學實驗求得軸位取代反應的觀測反應速率常數及形成反應速率，而其形成反應速率的大小依序為：N3- > SCN- > Cl- > Br-，與單牙配位基的鹼度大小順序一致；同時將logkf 對logKx作圖可得到一直線關係，在不同的反應溫度之下，此三條線的斜率分別為0.97(25℃)、0.96 (30℃)及0.91 (35℃)，表示過渡狀態時X-的性質與生成物非常相近，即X-在過渡狀態時已經和金屬產生了鍵結，所以此取代反應為一associative型式的交換反應機構；此結果與經由Eyring方程式所得到的負值△S≠相互得到印證。

The macrocyclic tetraamine ligand，1.4.8.11-tetraazacyclotetradecane (cyclam)，was obtained by template synthesis；mono-N-substituted tetraazamacrocyclic compound，1-(2-Pyridylmethyl)-1.4.8.11-tetraazacyclotetra- decane，was accomplished by reaction of a fivefold excess of cyclam with 1 equivalent of the alkylating reagent，2-chloromethylpyridine- hydrochloride。A six-coordinated complex was formed by Ni(ClO4)2.6H2O and this ligand。
Substitution reactions of [Ni (cyclam-CH2-Py)(H2O)]2+ with some monodentate ligands at different temperatures were studied by spectrophotometric method。Using the Rose Drago equation，we found that the equilibrium constants of these ligands decrease in the order N3- > SCN- > Cl- > Br-，and it was mainly effected by the basicity of these monodentate ligands。The softness and basicity of this Ni(II) complex could be quantitatively correlated by Edwards equation。According to the values of α，β andα/β obtained by Edwards equation，we could know that the character of this Ni(II) complex we used was between hard and soft acid。Furthermore，we used Eyring equation to analyze the character of the transition state。The negative values of ΔS≠ for different monodentate ligands showed an associative mechanism for these substitution reactions。
The observed rate constants kobsd of substitution reactions were obtained at different temperatures using stopped-flow method。The formation rate constants kf of these ligands decrease in the order N3- > SCN- > Cl- > Br-，consisting with basicities of the monodentate ligands。Plots of log kf against logKX at different temperatures gave slopes of 0.97 (25℃)、0.96 (30℃)及0.91 (35℃)，showing an associative mechanism for these substitution reactions。The equilibrum constants， KX，obtained by spectrophotometric method under equilibrum conditions were in agreement with kinetically determined values (kf/ksol)。

謝誌 I
中文摘要 III
Abstract V
目錄 VII
圖目錄 X
表目錄 XVI
第一章 緒論 1
第二章 四胺基大環配位子之設計及其鎳(II)錯合物之合成 14
一、前言 14
二、儀器與藥品 18
三、四胺基大環配位子之合成 18
第三章 大環四胺基鎳(II)錯合物與各種單牙配位基間之熱力學研究 26
一、前言 26
二、實驗部分 28
(一)試藥及溶液的配製 28
(二)儀器設備 28
(三)實驗方法 28
三、結果 29
(一)單牙配位陰離子對平衡常數的影響 47
(二)溫度對平衡常數的影響 49
(三)熱力學函數△S≠值 50
(四)錯合物之軟硬度研究 53
第四章 大環四胺基鎳(II)錯合物與各種單牙配位基間之動力學研究 57
一、前言 57
二、實驗部分 61
(一)試藥及溶液的配製 61
(二)儀器設備 61
(三)動力學測量方法 61
三、結果 62
四、討論 78
(一) 動力學平衡常數的研究 78
(二)進入基及離去基的影響 78
第五章 結論 84
參考資料 86

1. Moser, F. H.; Thomas, A. L. J. Chem. Educ. 1964, 41, 245.
2. Antonini, E.; Brunori, M. Hemoglobin and Myoglobin in Their Reaction with Ligand, Northhollard, Amsterdam, 1971.
3. Mark ; G. S. Heme and Chlorophylls, Van Nodtrand, London, 1975.
4. Smith, E. L. Vitamin B12, 3nd. Ed., Methneu, London, 1965.
5. Wang, J. H. Acc. Chem. Res. 1970, 1, 90.
6. Lemberg, R.; Barrett, J. Cytochromes, Academic Press, London, 1973.
7. Jones, D. R.; Lindoy, L. F.; Sargeson, A. M. J. Am. Chem. Soc. 1983, 105, 7327.
8. Stubbe, J.; Kozarich, J. W. Chem. Rev. 1987,87, 1107.
9. Chin, J.; Zou, X. J. Am. Chem. Soc. 1988, 110, 223.
10. Connolly, J. A.; Banaszczyk, M.; Hynes, R. C.; Chin, J. Inorg. Chem. 1994, 33, 665.
11. Cabbiness, D. K.; Margerum, D. W. J. Am. Chem. Soc. 1970, 92, 2151.
12. Martin, L. Y.; Dehayes, L. J.; Zompa, L. J.; Busch, D. H. J. Am. Chem. Soc. 1974, 96, 4048.
13. Fabbrizzi, L. J. Chem. Soc., Dalton Trans. 1979, 1857.
14. Hay, R. W.; Bembi, R. Inorg. Chem. Acta. 1982, 65, 1227.
15. Lin, C. T.; Rorabacher, D. B.; Cayley, G. R.; Margerum, D. W. Inorg. Chem. 1975, 14, 919.
16. Margerum, D. W.; Cayley, G. R.; Weatherburn, D. C.; Pagenkof, G. K. Coordination Chemistry, Vol. 2, Martell, A. E. Ed., American Chemistry Society, Washington D.C., 1978, No. 174, 1-220.
17. Hay, R. W.; Clark, C. R. J. Chem. Soc., Dalton Trans. 1977, 1148.
18. Turan, T. S.; Rorabacher, D. B. Inorg. Chem. 1990, 29, 2409.
19. Olson, D.C.; Vasilevskis, J. Inorg. Chem. 1969, 8, 1611.
20. Cabbiness, D. K.; Margerum, D. W. J. Am. Chem. Soc. 1969, 91, 6540.
21. Clay, R.; Corr, S.; Micheloni, M.; Paoletti, P. Inorg. Chem. 1985, 24, 3330.
22. Liang, B. F.; Chung, C. S. Inorg. Chem. 1981, 20, 2152.
23. Liang, B. F.; Chung, C. S. Inorg. Chem. 1983, 22, 1017.
24. Hertli, L.; Kaden, T. A. Helv. Chem. Acta. 1974, 57, 1328.
25. Lai, T. F.; Poon, C. K. Inorg. Chem. 1976, 15, 1562.
26. Chen, F. T.; Lee, C. S.; Chung, C. S. Polyhedron, 1983, 2, 1302.
27. paoletti, P.; Fabbrizzi, L.; Barucci, R. Inorg. Chem. 1973, 12, 1961.
28. Barefield, R. K.; Lovecchio, F. V.; Tokel, N. E.; Ochiai, E.; Busch, D. H. Inorg. Chem. 1972, 11, 283.
29. Kodama, M.; Kimura, E. J. Chem. Soc. Chem. Commun. 1975, 326.
30. Kodama, M.; Kimura, E. J. Chem. Soc. Chem., Dalton Trans. 1976, 116.
31. Anichini, A.; Fabbrizzi, L.; Paloetti, P.; Clay, R. M. J. Chem. Soc. Chem. Commun. 1977, 244.
32. Anichini, A.; Fabbrizzi, L.; Paloetti, P.; Clay, R. M. J. Chem. Soc. Chem. Commun. 1978, 577.
33. Warner, L. G.; Busch, D. H. J. Am. Chem. Soc. 1969, 91, 4092.
34. Dei, A. Inorg. Chem. 1979, 18, 891.
35. Kolinsky, R. A.; Korybut, D. B. Inorg. Chem. Acta. 1975, 14, 237.
36. Lee, C. S.; Wu, S. Y.; Chung, C. S. Inorg. Chem. 1984, 23, 1298.
37. Buxtorf, R.; Raden, T. A. Helv. Chem. Acta. 1974, 57, 1035.
38. Barfield, E. K.; Wabner, F. Inorg. Chem. 1975, 14, 296.
39. Bryan, P. S.; Dabrowiak, J. C. Inorg Chem. 1975, 28, 275.
40. Hay, R. W.; Lawrence, G. A. J. Chem. Soc. Dalton Trans, 1975, 1466.
41. Curtis, N. F.; Milestone, Aust. J. Chem. 1975, 28, 275.
42. Martin, J. G.; Cummings, S. C. Inorg. Chem. 1973, 12, 1477.
43. Cook, D. F.; Curtis, N. F.; Hay, R. W. J. Chem. Soc. Dalton Trans. 1973, 1160.
44. Palmer, J. M.. Papaconstantinou, E.; Endicott, J. F. Inorg. Chem. 1969, 8, 1516.
45. Curtis, Y. M.; Curtis, N. F. Aust. J. Chem. 1966, 19, 609.
46. Blight, M. M.; Curtis, N. F. J. Chem.Soc. 1962, 3016.
47. Curtis, N. F. J. Chem. Soc. Dalton Trans. 1973, 863.
48. Chung, C. S.; Hung, S. T. J. Chin. Chem. Soc. 1976, 23, 139.
49. Liou, M. C.; Chao, K. H.; Liang, B. F.; Chung, C. S. J. Chin. Chem. Soc. 1978, 25, 27.
50. Chao, K. H.; Liang, B. F.; Chung, C. S. J. Chin. Chem. Soc. 1979, 26, 93.
51. Liang, B. F.; Margerum, D. W.; Chung, C. S. J. Chin. Chem. Soc. 1979, 18, 93.
52. Liang, B. F.; Chung, C. S. Inorg. Chem. 1979, 18, 2001.
53. Wu, S. Y.; Lee, C. S.; Chung, C. S. Inorg. Chem. 1984, 23, 420.
54. Poon, C. K. Coord. Chem. Soc. 1954, 76, 1540.
55. Liang, B. F.; Chung, C. S. Inorg. Chem. 1980, 19, 572.
56. Lee, C. S.; Chung, C. S. Inorg. Chem. 1984, 23, 4162.
57. Liang, B. F.; Chung, C. S. J. Chem. Soc. Dalton Trans. 1980, 1349.
58. Guilard, R.; Rabiet, F.; Denat, F. Synthetic Communications,1997, 27, 979.
59. Guilard, R.; Lachkar, M.; Andrioletti, B. New J. Chem. 1995, 19, 777.
60. Holm, R. H.; Truex, T. J. J. Am. Chem. Soc. 1971, 93, 285.
61. Holm, R. H.; Truex, T. J. J. Am. Chem. Soc. 1972, 94, 4529.
62. Tang, S. C.; Weinstein, G. N.; Holm, R. H. J. Am. Chem. Soc. 1973, 95, 613.
63. Tang, S. C.; Koch, S.; Weinstein, G. N.; Lane, R. W.; Holm, R. H. Inorg.Chem. 1973, 12, 2589.
64. Koch, S.; Holm, R. H.; Frankel, R. B. J. Am. Chem. Soc. 1975, 97, 6714.
65. Busch, D. H. Rec. Chem. Prog. 1964, 25, 107.
66. Lindoy, L. F.; Busch, D. H. “ Preparative Inorganic Reactions “ ; vol.6 ; Interscience. New York, 1971.
67. Curtis, N. F. Coord. Chem. Rev. 1968, 3, 3.
68. Busch, D. H. Helv. Chem. Acta. 1967, 50, 174.
69. Lindoy, L. F.; Busch, D. H. Inorg. Chem. 1974, 13, 2494.
70. Thompson, M. C.; Busch, D. H. J. Am. Chem. Soc. 1964, 86, 3651.
71. Meunier, I.; Mishra, A. K.; Hanquet, B.; Cocolios, P.; Guilard, R. Can. J. Chem. 1995, 73, 685.
72. Studer, M.; Kaden, A. Helv. Chem. Acta. 1986, 69, 2081.
73. Drago, R. S. “Physical Methods in Inorganic Chemistry” W. B. Sounders Company; Philadelphia London Toronto. 1997, 95.
74. Lee, C. S. Ph. D. Thesis, National Tsing Hua University 1984.
75. Chen, J. W. Ph. D. Thesis, National Tsing Hua University 1986.
76. Wu, D. T. Ph. D. Thesis, National Tsing Hua University 1986.
77. Liang, B. F. Ph. D. Thesis, National Tsing Hua University 1980.
78. Edwards, J. O. J. Am. Chem. Soc. 1954, 76, 1540.
79. Liang, B. F.; Peng, T. H. and Chung, C. S. J. Inorg. Nucl. Chem., 1981, 43, 1671.
80. Pearson, R. G. Science, 1966, 151, 172.
81. Lee, T. J.; Lee, T. Y.; Juang, W. B. and Chung, C. S. Acta. Cryst, 1985, C41, 1745.