臺灣博碩士論文加值系統

由[a-Ni(tetb)(Y)]ClO4之晶體構造圖以及JOB氏連續變化法研究等證據，顯示在有機溶劑中此錯合物為一五配位三角雙錐之構造。其原因為Ni(II)上之大環配位子受到溶劑分子的擠壓所致，因此形成一五配位三角雙錐之構造，進而能與一價陰離子進行軸位取代反應。
由動力學及熱力學實驗得知，此反應為一Id型態之反應機構，表示進入基與過渡態之活化複合體並無鍵結形成。影響形成速率常數與平衡常數的主要原因有：
(1)若變換不同的有機溶劑，則此軸位取代反應之速率常數以及平衡常數會受到溶劑的介電常數值及空間立體障礙的影響。在以DMF、DMSO及CH3CN為溶劑的情況下其平衡常數之大小順序為：
KY (DMF) > KY (DMSO) > KY (CH3CN)
(2)若在相同的溶劑情況下，則此軸位取代反應之速率常數及平衡常數的大小主要是受到陰離子的半徑所影響。其平衡常數之大小順序為： I-＜Br-＜Cl-，N3-
而陰離子半徑是影響溶劑對陰離子的媒合作用(Solvation)的主要因素，因此當錯合物在溶劑中與陰離子要進行取代反應時，則必須先要除去媒合作用(desolvation)，所以陰離子媒合作用越大對軸位取代反應之速率常數及平衡常數則越為不利。
綜合以上的結論研究了大環錯合物在錯合反應上種種作用與變化情形，以期能提供生物體系內大環錯合物之無機化學方面一些有價值的參考。

Abstract
The square planar complex ion, Ni(C-rac-1,7-CTH)2+ (1,7-CTH = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacycloteradecane or tetb), theoretically can exist in 10 diasteredisomers, depending on the configurations of the four asysmmetric secondary amine center. The synthesis, characterization, x-ray structural and conformation studies of the five isomers were reported. Among these the molecular model of α-Ni(C-rac-1,7-CTH)2+ isomer indicates that the two axial sites are quite open and accessible to small monodentate ligands, as the methyl groups attached to the asymmetric carbons are all equatorial. According to Bosnich etal, the complex ionα-Ni(C-rac-1,7-CTH)2+, possesses trans-V configuration. With bidentate or even strong monodenate ligands, this isomeric form affords the cis-derivatives with the macrocyclic ligand is in folded state. Equilibrium constants and five coordinated ligand substitution kinetic studies on Cu(C-rac-1,7-CTH)2+ with monodentate ligands had been published. The study of substitution reaction in five coordinated complexes has given attention because they exist an intermediate state, in both a kinetic and steric sense, between the four coordinates complexes which are open to nucleophilic attack and the six coordinated systems which are not. In case of five coordinated complexes, both associative and dissociative mechanisms are possible by heiter added or lose of an monodentate ligands. In aprotic solvent the equilibrium constants for the reaction of Ni(TMC)2+ with halide ions reported. Here we report equilibrium constants for the reactions of α-Ni(C-rac-1,7-CTH)2+ with halide ion in aprotic solvents by kinetic and spectrophotometric methods and the x-ray crystal structure of five coordinated α-[Ni(C-rac-1,7-CTH)(Cl)](ClO4) complex.

目 錄
目錄----------------------------------------------------------Ⅰ
中文摘要------------------------------------------------------Ⅶ
第一章緒論-------------------------------------------------1
第二章二價鎳與四胺基大環配位子之錯合物合成----------------16
第三章二價鎳大環四胺基錯合物與一價陰離子軸位取代反應之動力學研究---------------------------------------------------------28
一、前言------------------------------------------------28
二、實驗部分--------------------------------------------33
三、結果------------------------------------------------35
四、討論------------------------------------------------42
第四章二價鎳大環四胺基錯合物與一價陰離子軸位取代反應之熱力學研究---------------------------------------------------------45
一、前言------------------------------------------------45
二、實驗部分--------------------------------------------49
三、結果------------------------------------------------51
四、討論------------------------------------------------60
第五章 總結---------------------------------------------------62
參考文獻------------------------------------------------------63

參考文獻
1.Moser, F. H.; Thomas, A. L. J. Chem. Educ. 1964, 41, 245.
2.Antonini, E.; Brunori, M. Hemoglobin and Myolobin in Their Reaction with Ligand, Northhollard, Amsterdam, 1971.
3.Mark; G. S. Heme and Chlorophylls, Van Nostrand, 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. Chim. Acta 1982, 65, L227.
15.Cabbiness, D. K.; Margerum, D. W. J. Am. Chem. Soc. 1969, 91, 6540.
16.Lin, C. T.; Rorabacher, D. B.; Cayley, G. R.; Margerum, D. W. Inorg. Chem. 1975, 14, 919.
17.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.
18.Busch, D. H. Rec. Chem. Prog. 1964, 25, 107.
19.Busch, D. H. Helv. Chim. Acta. 1967, 50, 174.
20.Christensen, J. J.; Hill, J.O.; Izatt, R. M. Science. 1971, 174, 459..
21.Pedersen, C. J.; Frendsdroff, H. H. Angew. Chem. Int. Ed. Engl. 1972, 11, 16.
22.Black, D. St. C.; Harshorn, A. J. Coord. Chem. Rev. 1972, 9, 219.
23.Lehn, L. M. Structure and Bonding. 1973, 16, 1.
24.Olson, D. C.; Vasilevskis, J. Inorg. Chem. 1971, 10, 463.
25.Olson, D. C.; Vasilevskis, J. Inorg. Chem. 1969, 8, 1611.
26.Tokel, N. E.; Katovic, V.; Anderson, L. B.; Busch, D. H. J. Am. Chem. Soc. 1970, 92, 400.
27.Izatt, R.M; Eatough, D. J.; Curtis, N. F. J. Chem. Soc. Perkin. Trans. 1975, 1, 591.
28.Beinert, H. Coord. Chem. Rev. 1977, 23, 119.
29.Sakaguchi, U.; Addison, A. W. J. Chem. Soc. Dalton Trans. 1979,1458.
30.Gillard, R. D. Inorg. Chim. Acta Rev. 1967, l, 69.
31.Steinhaus, R. K.; Margerum, D. W. J. Am. Chem. Soc. 1966, 88, 441.
32.Margerum, D. W.; Rosen, H. M. J. Am. Chem. Soc. 1967, 89, 1088.
33.Cobb, M. A.; Hague, D. N. J. Am. Chem. Soc., Faraday Trans. 1 1972, 86, 932.
34.Curtis, N. F. J. Chem. Soc. 1964, 2644.
35.Holm, R. H.; Truex, T. J. J. Am. Chem. Soc. 1971, 93, 285.
36.Truex, T. J.; Holm, R. H. J. Am. Chem. Soc. 1972, 94, 4529.
37.Sharma, V. S.; Leussing, D. L. J. Chem. Soc., Chem. Commun. 1970, 1278.
38.Sharma, V. S.; Leussing, D. L. Inorg. Chem. 1972, 11, 138.
39.Hauer, H.; Billo, E. J.; Margerum, D. W. J. Am. Chem. Soc. 1971, 93, 4173.
40.Cobb, M. A.; Hague, D. N. J. Chem. Soc, Chem. Commun. 1971, 192.
41.Martin, L. Y.; Sperati, C. R.; Busch, D. H. J. Am. Chem. Soc. 1977, 99, 2628.
42.Chung, C. S; Hung, S. T. J. Chin. Chem. Sco. 1976, 23, 139.
43.Liou, M. C; Chao, K. H.; Liang, B. F.; Chung, C. S. J. Chin. Chem. Soc. 1978, 25, 27.
44.Liang, B. F.; Chao, K. H.; Liang, B. F. J. Chin. Chem. Soc. 1979, 26, 93.
45.Liang, B. F.; Margerum, D. W.; Chung, C. S. J. Chin. Chem. Soc. 1979, 18, 93.
46.Liang, B. F.; Chung, C. S. Inorg. Chem. 1979, 18, 2001.
47.Wu, S. Y.; Lee, C. S.; Chung, C. S. Inorg. Chem. 1984, 23, 420.
48.Lee, C. S. Ph. D. Thesis, National Tsing Hua University 1984.
49.Poon, C. K. Coord. Chem. Rev. 1973, 10, 1.
50.Edwards, J. O. J. Am. Chem. Soc. 1954, 76, 1540.
51.Liang, B. F.; Chung, C. S. Inorg. Chem. 1980, 19, 572.
52.Liang, B. F.; Peng, T. H.; Chung, C. S. J.Inorg. Nucl. Chem. 1981, 43, 1671.
53.Lee, C. S.; Chung, C. S. Inorg. Chem. 1984, 23, 4162.
54.Liang, B. F.; Chung, C. S. J. Chem. Soc. Dalton Trans. 1980, 1349.
55.Lee, C. S.; Chung, C. S. Inorg. Chem. 1984, 23, 4162.
56.Lee, C. S.; Wang, G. T.; Chung, C. S. J. Chem. Soc. Dalton. Trans. 1984, 109.
57.Martin, L. Y.; Dehayes, L. J.; Zompa, L. J.; Busch, D. H. J. Am. Chem. Soc. 1974, 96, 4048.
58.Bhattacharya, P. K. J. Inorg. Nucl. Chem. 1981, 43,41.
59.Fabbrizzi, L. J. Chem. Soc. Dalton Trans. 1979, 1857.
60.Cabbiness, D. K.; Margerum, D. W. J. Am. Chem. Soc. 1969, 91, 6540.
61.Fabbrizzi, L.; Paoletti, P.; Lever, A. B. P. Inorg. Chem. 1976, 15, 1502.
62.Hinz, F. P.; Margerum, D. W. Inorg. Chem. 1974, 13, 2941.
63.Hertli, L.; Kaden, T. A. Helv. Chim. Acta. 1974, 57, 1328.
64.Cabbiness, D. K.; Margerum, D. W. J. Am. Chem. Soc. 1970, 92, 2151.
65.Jones, T. E.; Roabacher, D. B.; Ochrymowycz, L. A. J. Am. Chem. Soc. 1975, 97, 7485.
66.Jones, T. E.; Zimmer, L. L.; Diaddario, L. L.; Rorabacher, D. B.; Ochrymowycz, L. A. J. Am Chem. Soc. 1975, 97, 7163.
67.Liang, B. F.; Chung, C. S. Inorg. Chem. 1981, 20, 2152.
68.Liang, B. F.; Chung, C. S. Inorg. Chem. 1983, 22, 1017.
69.Lin, C.T.; Rorabacher, D. B.; Cayley, G. R.; Margerum, D. W. Inorg. Chem. 1975, 14, 919.
70.Chung, C. S. PH. D. Thesis, Purdus University 1974.
71.Hay, R. W.; Clark, C. R. J. Chem. Soc. Dalton Trans. 1977, 1148.
72.Chen, F. T.; Lee, C. S.; Chung, C. S. Polyhedron 1983, 2, 1301.
73.Lai, T. F.; Poon, C. K. Inorg. Chem. 1976, 15, 1562.
74.Curtis, N. J.; Hendry, P.; Lawrance, G. A. J. Chem. Soc. Dalton Trans., 1988, 47.
75.Paoletti, P.; Fabbrizzi, L,; Barucci, R. Inorg, Chem. 1973, 12, 1961.
76.Barefield, R. K.; Lovecchio, F. V.; Tokel, N. E.; Ochiai, E.; Busch, D. H. Inorg. Chem. 1972, 11, 283.
77.Kodama, M.; Kimura, E. J. Chem. Soc. Chem. Commun. 1975, 326.
78.Kodama, M.; Kimura, E. J. Chem. Soc. Dalton Trans. 1976, 116.
79.Clay, R. M.; Corr, S.; Micheloni, M.; Paoletti, P. Inorg. Chem. 1985, 24, 3300.
80.Anichini, A.; Fabbrizzi, L.; Paloetti, P.; Clay, R. M. J. Chem. Soc. Chem. Commun. 1977, 244.
81.Gallori, E.; Martini, E.; Micheloni, M.; Paoletti, P. J. Chem. Soc.Dalton Trans, 1980, 1722.
82.Anichini, A.; Fabbrizzi, L.; Paloetti, P.; Clay, R. M. J. Chem. Soc. Dalton Trans. 1978, 577.
83.Clay, R. M.; Mccormac, H.; Micheloni, M.; Paoletti, P. Inorg. Chem. 1982, 21, 2494.
84.Clay, R. M.; Micheloni, M.; Paoletti, P.; Steele, W. V. J. Am. Chem. Soc. 1979, 101, 4419.
85.Pasternack, R. F.; Angwin, M.; Gipp. L.; Reingold, R. J. Inorg. Nucl. Chem, 1972, 34, 2329.
86.Warner, L. G.; Busch, D. H. J. Am. Chem.Soc. 1969, 91, 4092.
87.Dei, A. Inorg. Chem. 1979, 18, 891.
88.Kolinsky, R. A.; Korybut, D. B. Inorg. Chim. Acta 1975, 14,237.
89.Lee, C. S.; Wu, S. Y.; Chung, C. S. Inorg. Chem. 1984, 23, 1298.
90.Buxtorf, R.; Raden, T. A. Helv. Chim. Acta 1974, 57, 1035.
91.Wagner, F.; Barefield, E. K. Inorg, Chem. 1976, 15, 408.
92.Barefield, E. K.; Wabner, F. Inorg. Chem. 1973, 12, 2435.
93.Bryan, P. S.; Dabrowiak, J. C. Inorg. Chem. 1975, 14, 296.
94.Curtis, N. F.; Milestone, Aust. J. Chem. 1975, 28, 275.
95.Hay, R. W.; Lawrence, G. A. J. Chem. Soc. Dalton Trans. 1975, 1466.
96.Martin, J. G.; Cummings, S. C. Inorg. Chem. 1973, 12, 1477.
97.Cook, D. F.; Curtis, N. F.; Hay, R. W. J. Chem. Soc. Dalton Trans. 1973, 1160.
98.Palmer, J. M. Papaconstantinou, E.; Endicott, J. F. Inorg. Chem. 1969, 8, 1516.
99.Curtis, Y. M.; Curtis, N. F. Aust. J. Chem. 1966, 19, 609.
100.Blight, M. M.; Curtis, N. F. J. Chem. Soc. 1962, 3016.
101.Curtis, N. F. J. Chem. Soc. Dalton Trans. 1973, 863.
102.Holm, R. H.; Truex, T. J. J. Am. Chem. Soc. 1971, 93, 285.
103.Truex, T. J.; Holm, R. H. J. Am. Chem. Soc. 1972, 94, 4529.
104.Tang, S. C.; Weinstein, G. N.; Holm, R. H. J. Am. Chem. Soc. 1973, 95, 613.
105.Tang, S. C.; Koch, S.; Weinstein, G. N.; Lane, R. W.; Holm, R. H. Inorg. Chem. 1973, 12, 2589.
106.Koch, S.; Holm, R. H.; Frankel, R. B. J. Am. Chem. Soc. 1975, 97, 6714.
107.Honeybourne, C. L. Inorg. Nuch. Chem. Lett. 1975, 11, 191.
108.Martin, L. Y.; Sperti, C. R.; Busch, D. H. J. Am. Chem. Soc. 1977, 99, 2968.
109.Busch, D. H. Rec. Chem Prog. 1964, 25, 107.
110.Lindoy, L. F.; Busch, D. H. "Preparative Inorganic Reactions" Vol. 6.; Interscience. New York, 1971.
111.Black, D. St. C. Pure and Appl. Chem. 1965, 15, 109.
112.Lindoy, L. F.; Busch, D. H. Inorg. Chem. 1974, 13, 2494.
113.Thompson, M. C.; Busch, D. H. J. Am. Chem. Soc. 1964, 86, 3651.
114.Chen, J. W.; Wu, D. T.; Chung, C. S. Inorg.Chem. 1986, 25, 863.
115.Inczedy, J. "Analytical Applications of Complex Equilibria", Tyson, J. 1976, Chapter 2.
116.Job, P. Ann. Chim Phys. 1928, 9, 113.