臺灣博碩士論文加值系統

Trans-(isn)(NH3)4Ru(pz)Fe(CN)5-雙核錯合物(I)可藉trans-Ru(NH3)4(isn)(pz)2+與等mole數之
Fe(CN)5OH23-在pH＝5溶液中作用而得，trans-(isn)(NH3)4Ru(pz)Fe(CN)5(II)混價雙核錯合物則是將
trans-(isn)(NH3)4Ru(pz)Fe(CN)5-溶液以一當量S2O82-氧化而得。吸收光譜顯示雙核錯合物I及II在可見光區均有MLCT吸收，且相對於單核M(II)錯合物均有紅位移現象。電化學結果顯示雙核錯合物呈現兩組單電子可逆氧化還原波，E1/2＝0.58 V和0.88 V ( vs NHE )分別屬於[ Ru(II),Fe(III) ]/[ Ru(II),Fe(II) ]及
[ Ru(III), Fe(III) ]/[ Ru(II), Fe(III) ]之還原電位 。UV-Vis光譜及電化學結果顯示混價分子(II)屬於定域性Ru(II)/Fe(III)之金屬氧化態。從電化學結果求得之comproportionation constant, Kc顯示，相對於isovalent states，混價分子有3.5 kcal mol -1之額外穩定能。混價分子價間吸收光譜性質符合Hush理論。

The binuclear complex trans-(isn)(NH3)4Ru(pz)Fe(CN)5- (I) was prepared by mixing the equimolar of trans-Ru(NH3)4(isn)(pz)2+ and Fe(CN)5OH23- in pH=5 aqueous solution. The mixed valence complex trans-(isn)(NH3)4Ru(pz)Fe(CN)5 (II) was obtained by the oxidation of (I) with one equivalent peroxy disulfate ion. The absorption spectra of I and II both show a MLCT absorption in the visible region with significant bathochromatic shifts as compare to the mononuclear Ru(II) and Fe(II) complexes. The cyclic voltammogram of II exhibits one electron reversible waves with E1/2＝0.58 and 0.88 V( vs. NHE) which correspond to [ Ru(II),Fe(III) ]/[ Ru(II),Fe(II) ] and [ Ru(III), Fe(III) ]/[ Ru(II), Fe(III) ] complexes, respectively. The results of aborption spectrum and electrochemistry both suggest that the mixed valence compound features valence trapped localized and Ru(II), Fe(III) oxidation states. The comproportionation constant Kc calculated from the result of electrochemistry shows an additional stability of 3.5 kcal mol -1 relative to its isovalent states.
The properties of intervalence band (λmax＝1280 nm) the mixed valence molecule agree with Hush’s theory.

總目錄

中文摘要 I
英文摘要 II
總目錄 III
圖目錄 V
表目錄 VI
第一章 序論 1
第二章 實驗 9
一. 藥品名稱及來源 9
二. 藥品純化及溶液配製 10
三. 去氧處理 12
四.錯合物合成 14
五. 分析方法 20
第三章 結果與討論 24
1. 吸收光譜 24
2. 氧化動力學 29
3. 電化學 35
4. 價間吸收光譜 37
第四章 結論 44
參考文獻 45

1. A. Werner, Z. Anorg. Chem. 12, 53 (1896)
2. M. B. Robin, Inorg. Chem.1, 337 (1962)
3. E. S. Gould, H. Taube, Acc. Chem. Res. 2, 321 (1969)
4. H. Taube, Surv. Prog. Chem. 6, 1 (1973)
5. P. Ford, DeF. P. Rudd, R. Gaunder, H. Taube, J. Am. Chem. Soc. 90, 1187 (1968)
6. C. Creutz, H. Taube, J. Am. Chem. Soc.91, 3988 (1969)
7. C. Creutz, H. Taube, J. Am. Chem. Soc.95, 1086 (1973)
8. B. Mayoh, P. Day, J. Am. Chem. Soc.94, 2885 (1972)
9. C. Creutz, M. Good, S. Chandra, Inorg. Nucl. Chem. Lett. 9, 171 (1973)
10. I. M. Treitel, Ph. D. Thesis, California Institute of Technology, 1970
11. T. Strekas, T. Spiro, Inorg. Chem. 15, 974 (1976)
12. J. H. Elias, R. Drago, Inorg. Chem.11, 415 (1972)
13. P. H. Citrin, J. Am. Chem. Soc.95, 6472 (1973)
14. J. K. Beatie, N. S. Hush, P. R. Taylor, Inorg Chem. 15, 992 (1976)
15. H. Taube, Ann. New York Aca. Sci. 313, 481 (1978)
16. J. E. Sutton, H. Taube, Inorg Chem. 20, 3125 (1981)
17. D. E. Richardson, H. Taube, J. Am. Chem. Soc.105, 40 (1983)
18. H. E. Toma, J. M. Malin, Inorg. Chem. 12, 1039 (1973)
19. F. Felix, A. Ludi, Inorg. Chem. 17, 1782 (1978)
20. A. Yeh, A. Haim, J. Am. Chem. Soc. 107, 369(1985)
21. H. Y. Huang, W. J. Chen, C. C. Yang, A. Yeh, Inorg. Chem. 30, 1862 (1991)
22. G. Tsaur, M. C. Wu, A. Yeh, J. Chin. Chem. Soc. 41, 431 (1994)
23. C. L. Lin, K. Huang, A. Yeh, H. T. Tsen, C. C. Su, Inorg. Chem. 38, 411 (1999)
24. S. Isied, H. Taube, Inorg. Chem. 13, 1545 (1974)
25. S. Isied, H. Taube, Inorg. Chem. 15, 3070 (1976)
26. D. M. Stanbury, O. Haas, H. Taube, Inorg. Chem. 19, 518 (1980)
27. G. Brauer, “Handbook of prepartive Inorganic Chemistry”, Vol. 2,
and ed. Academic Press, New York, N. Y., 9, 1511 (1965)
28. J. J. Jwo, A. Haim, J. Chin. Chem. Soc. 98, 1172 (1976)
29. D. W. Franco, H.Taube, Inorg. Chem. 17, 571 (1978)
30. M. H. Chen, S. Lee, S. Liu, A. Yeh, Inorg. Chem. 35, 2627 (1996)
31. D. M. Stanburg, Adv. Inorg. Chem. 33, 70 (1989)
32. N. S. Hush, Prog. Inorg. Chem. 8, 391 (1967)