研究生: |
梅剛平 bell mei |
---|---|
論文名稱: |
2-胺基本甲醛、2-胺基苯甲酮與2-胺基苯甲酸之大環錯合物的合成、結構及光譜性質研究 The study with macrocyclic coordnation compounds form by 2-aminobenzaldehyde and its derivatives. |
指導教授: |
蘇展政
Su, Chan-Cheng |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2001 |
畢業學年度: | 89 |
語文別: | 中文 |
中文關鍵詞: | 2-胺基苯甲醛 、2-胺基苯甲酮 、2-胺基苯甲酸 |
英文關鍵詞: | 2-aminobenzaldehyde, 2-aminobenzoic acid |
論文種類: | 學術論文 |
相關次數: | 點閱:121 下載:0 |
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中 文 摘 要
本研究以2-胺基苯甲醛 (2-aminobenzaldehyde) 、2-胺基苯甲酮(2-aminoacetophenone)、2-胺基苯甲酸 (2-aminobenzoic acid) 為主要配子,合成了十六環四牙基錯合物與十二環三牙基錯合物,十六環四牙基錯合物有[Cu(TAAB)](NO3)2、[Cu(TAAB)](BF4)2、[Fe(TAAB)](FeCl4);十二環三牙基錯合物有[Cu(TRI)(CH3CN)](CF3SO3)、[Ni(TRI)(H2O)2(NO3)](NO3)、[Cu(TRI)(CH3CN)](BF4)、[Co(TRI)(H2O)](NO3)2、[Cu(TRI-OCH3)(CH3CN)](CF3SO3)、[Cu(TRI)2](BF4)2.H2O、[Cu(TRI-Me3)]2O2(BF4)2.7H2O、[Cu(C21H14N3O3-)]2O2.6H2O.CH3CN、[Cu(C27H26N3O9-)]2O2.3H2O。利用元素分析、紅外光光譜、紫外光-可見光吸收光譜、質譜儀、電子順磁共振光譜及X-光單晶結構解析等方法,完成錯合物的結構鑑定及鍵結性質之探討。
目前已有X-光單晶結構解析的錯合物有:
1. [Cu(TAAB)](CF3SO3)2
屬於三斜晶系(triclinic),空間群為P,晶格常數a = 7.991(2) Å,b = 13.877(3)Å,c = 15.98(1)Å,α = 114.46(3)∘,β = 97.9(3)∘,γ = 102.52(2)∘,每單位晶格內含有2個分子(Z = 2),精算值 R = 0.134,RW = 0.149。
2. [Cu(TAAB)](BF4)2
屬於單斜晶系(monoclinic),空間群為P21/n,晶格常數a = 11.830 (2) Å,b = 13.380(2)Å,c = 16.737(3)Å,β = 92.82(2)∘,每單位晶格內含有4個分子(Z = 4),精算值 R = 0.086,RW = 0.085。
由X-光單晶結構解析可得知:兩個具有共軛雙鍵系統十六環四牙基的錯合物,因陰離子大小不同,造成結構上的不同,一個接近雙三角錐形體,另一個為四角錐形體。另外合成出來的具有共軛雙鍵系統三牙基錯合物:[Cu(TRI)(CH3CN)](CF3SO3)、[Cu(TRI)(CH3CN)](BF4)、[Cu(CH3O-TRI)(CH3CN)](CF3SO3),進行通氧實驗,從電子光譜判斷推論此過氧化物符合m-h2:h2-peroxo鍵結模式,顯示得到室溫下存在的血青素模型錯合物。而由 2-胺基苯甲酸(2-aminobenzoic acid)與一價銅的錯合物與氧反應,從電子光譜來判斷,亦形成m-h2:h2-peroxo的錯合物。
Abstract
This study deals with macrocyclic coordnation compounds formed by the metal-templated self-condensation reactions of 2-aminobenzaldehyde and its derivatives. The complexes,which include [Cu(TAAB)](NO3)2 , [Cu(TAAB)](BF4)2 , [Fe(TAAB)]-FeCl4 , [Cu(TRI)(CH3CN)](CF3SO3) , [Ni(TRI)(H2O)2(NO3)](NO3) , [Cu(TRI)(CH3CN)](BF4) , [Co(TRI)(H2O)](NO3)2 , [Cu(TRI-OCH3)(CH3CN)](CF3SO3) , [Cu(TRI)2](BF4)2.H2O , [Cu(TRI-Me3)]2O2(BF4)2.7H2O,[Cu(C21H14N3O3-)]2O2.6H2O.CH3CN and [Cu(C27H26N3O9-)]2O2.3H2O, have been prepared by several synthetic approaches,and characterized by elemental analyses , infrared , electronic , mass and epr spectroscopic measurements .
By using single-crystal X-ray diffraction method , the crystal and molecular structures of [Cu(TAAB)](CF3SO3)2 and [Cu(TAAB)](BF4)2 have been determined . Their crystal data are described below :
1. [Cu(TAAB)](CF3SO3)2 crystallizes in the triclinic , space group Pwith a = 7.991(2) Å , b = 13.877(3)Å , c = 15.98(1)Å , α = 114.46(3)∘, β = 97.9(3)∘, γ = 102.52(2)∘, Z = 2 , R = 0.134 and RW = 0.149 .
2. [Cu(TAAB)](BF4)2 crystallize in the monoclinic , space group P21/n with a = 11.830 (2) Å , b = 13.380(2)Å , c = 16.737(3)Å , β = 92.82(2)∘, Z = 4 , R = 0.086 and RW = 0.085 .
Both complexes coordinated by a saddle shaped TAAB with an approximate S4 symmetry , and an anion on the axial site to form a distorted square pyramid stucture. The copper ion is generally located in the middle of the N4 plane . Average copper-nitrogen distances were found to be 1.937Å – 1.966Å for [Cu(TAAB)](CF3SO3)2 , 1.975Å – 2.039Å for [Cu(TAAB)](BF4)2 .
Based on electronic spectroscopic data, the reactions of [Cu(TRI)(CH3CN)](CF3SO3)、[Cu(TRI)(CH3CN)](BF4)、[Cu(CH3O-TRI)(CH3CN)](CF3SO3) with dioxygen suggest the formation (m-h2:h2-peroxo)dicopper (II) complexes. Similar reactions are also observed for complexes of 2-aminoacetophenone.
參考文獻
1. Smith, L. I.; Opie, J. W. in Organic syntheses collective volume 3, 1963, 56-58.
2. Magnus , K. A.; Ton-That, H. J. Carpenter, J. E. in Bioinorganic Chemistry of Copper, Karlin, K. D; Tyeklar, Z. Eds., Champman & Hall, New York, 1993, p143-p150.
3. (a)Dooley, D. M.; Scott, R. A.; Ellinhaus, J.; Soloman, E. I.; Gary, H. B. Proc. Natl. Acas. Sci. U. S. A., 1978, 75,3019. (b)Moss, T. H.; Gould, D. C.;Enreberg, A.; Loehr, J.S.; Mason, H. S.; Biochemistry, 1973, 12, 2444.(c)Soloman, E. I.; Dooley, D. M.; Wang, R. H.; Gary, H. B.; Cerdonio, M.; Mogno, F.; Roman, G. L. J. Am. Chem. Soc., 1976, 98, 1029.
4. Magnus, K. A.; Ton-That, H.; Carpenter, J. E. in Bioinoganic Chemistry of Copper, Karlin, K. D.; Tyeklar, Z. Eds. Chapman & Hall, New York, 1993, p3-4.
5. (a)Kitaajma, N.; Fujisawa, K.; Moro-oka, Y.; Toriumi, K. J. Am. Chem. Soc., 1989, 111, 8975.(b)Kitajima, N.; Fujisawa, K.; Fujimoto, C.; Moro-oka, Y.; Hashimoto, S.; Kitagawa, T.; Toriumi, K.; Tatsumi, K.; Nakamura, A. J. Am. Chem. Soc., 1992, 114, 1277.
6. Tolman, W. B. Acc. Chem. Res., 1997, 30, 227-237.
7. Kolchinski, A. G. Coord. Chem. Rev., 1998, 174, 207-239.
8. Schindler, S.; Szalda, D. J. Inorg. Chim. Acta, 1995, 228,
93-101.
9. Jircitano, A. J.; Sheldon, R. I.; Mertz, K. B. J. Am. Chem. Soc., 1983, 105, 3022-3027.
10. Kamenar, B.; Kaitner, B.; Katovic, V.; Busch, D. H. Inorg. Chem, 1979, 18, 3, 815-818.
11. Jircitano, A. J.; Sheldon, R. I.; Beno, M. A.; William, J. M.; Mertz, K. B. J. Am. Chem. Soc., 1983, 105, 3028-3031.
12. Purcell, K. F.; Kotz, J. C. in Inorganic Chemistry, Saunder, W. B. Philadelphia, 1977.
13. Musker, W.; Huaasim, M. S., Inorg. Chem. Nucl. Chem.,1967, 3, 271.
14. Olsen, C. D.; Basu, G.; Belford, R. L. J. Coord. Chem., 1971, 1, 17.
15. Harrison, D. H.;Kebbedy, D.; Hathaway, B., J. Inorg. Nucl. Chem. Lett., 1981, 17, 87.
16. Hathaway, B. J.; Billing, D. E., Coord. Chem. Rev., 1970, 5, 143.
17. Mcgeachin, S. G. Canadian J. of Chem., 1966, 44, 2323-2328.
18. Robinson, B.; Zubair, M. U. Tetrahedron, 1973, 29, 1429-1432.
19. Taylor, L. T.; Vergez, S. C.; Busch, D. H. J. Am. Chem. Soc., 1966, 88, 3170-3171.
20. Cummings, S. C.; Busch, D. H. J. Am. Chem. Soc., 1970, 92, 1924-1934.
21. Melson, G. A.; Busch, D. H. J. Am. Chem. Soc., 1964, 86, 4834-4837.
22. Pang, I. W.; Stynes, D. V. Inorg. Chem., 1977, 16, 9, 2192-2199.
23. Shakir, M.; Omar, S.; Nasman, M.; Mohamed, A. K.; Varkey, S. P. Polyhedron, 1996, 15, 17, 2869-2873.
24. Melson, G. A.; Busch, D. H. J. Am. Chem. Soc., 1965, 87, 1706-1710.
25. Saito, Y.; Takemoto, J.; Hutchinson, B.; Nakamoto, K. Inorg. Chem. 1970, 11, 2003.
26. Jircitano, A. J.; Timken, M. D.; Mertes, K. B.; Ferraro, J. R. J. Am. Chem. Soc., 1979, 101, 7661.
27. Jircitano, A. J.; Colton, M. C.; Mertes, K. B. Inorg. Chem. 1981, 20, 890.
28. Jircitano, A. J.; Rohly, W. G.; Mertes, K. B. J. Am. Chem. Soc., 1981, 103, 4879.
29. Aggarual, R. C.; Singh, R. P. Inorg. Chem., 1985, 20, 2794.