本實驗以柳亞苯丙胺酸（sal-phe），5-硝基柳亞苯丙胺酸（nitro-sal-phe）及3-甲氧基柳亞苯丙胺酸（methoxy-sal-phe）為主配子，成功地合成了一系列四價釩的錯合物──VO(sal-D-phe)(L)，VO(sal-L-phe)(L) ，VO(nitro-sal-D-phe)(L)， VO(nitro-sal-L-phe)(L) 及VO(methoxy-sal-L-phe)(L)其中L為雙牙基或單牙基。雙牙基有1,10-二氮雜菲（1,10-phenanthroline），聯啶（bipyridine），及4,7二甲基-二氮雜菲（4,7dimethyl-phenanthroline）而單牙基為H2O，ROH。
利用元素分析，紅外線光譜，紫外光可見光光譜，電子順磁光譜，圓形二色光光譜，環伏安法及Ｘ-光結構解析方法完成錯合物結構的鑑定及鍵結性質的探討。
目前已完成X-光單晶結構解析的四價釩錯合物有：
(1)[VO(sal-D-phe)(OCH3)(HOCH3)]
斜方晶系（Orthorhombic），空間群為P21212，其晶格常數為：a=14.3954(4) A，b=18.9384(7) A，c=6.7507(2) A，V=1840.42(10) A3，Z=4，精算值為R=0.0534，wR2=0.1075
(5) (2)[VO(sal-D-phe)(H2O)]
單斜晶系（Monoclinic），空間群為P21，其晶格常數為：a=14.3954(4) A，b=18.9384(7) A，c=6.7507(2) A，=90o，=107.897(6)o ，=90o，V=795.9(3) A3，Z=2，精算值為R=0.0536，wR2=0.0847
(3)[VO(sal-L-phe)(OC9H9)(HOC9H9)]
單斜晶系（Monoclinic），空間群為P21，其晶格常數為：a=12.73800(10)A， b=7.9986(2)A，c=16.1993(3)A，=90o，=110.6570(6)o，=90o ，V=1544.375(3) A3，Z=2，精算值為R=0.0839 , wR2=0.1603
(4)[VO(methoxy-sal-L-phe)(dmphen)](H2O)
單斜晶系（Monoclinic），空間群為P21，其晶格常數為：a=6.3312(2)A；b=20.1158(6)A；c=11.1132(3)A，=90o，=98.1580(10)o ，=90o，V=1403.29(7) A3，Z=2，精算值為
R=0.0694 , wR2=0.1298
從晶體結構，EPR光譜，UV-VIS光譜和CD光譜可得知 [VO(sal-phe) (L)]，[VO(nitro-sal-phe)(L)] 和[VO(methoxy-sal-phe)(L)]系列錯合物結構為扭曲八面體結構。且經由可見光光譜高斯交疊解析與CD光譜高斯交疊解析綜合結果分析，可得知[VO(sal-pheH)(OCH3)(HOCH3)]和[VO(nitro-sal-pheH)(OCH3)(HOCH3)]的d軌域能階分裂為：dz2＞dyz＞dxz＞dx2-y2＞dxy，而[VO(sal-phe)(NN)] 的d軌域能階分裂為：dz2＞dyz＞dx2-y2＞dxz＞dxy。
　　並且針對所合成的不對稱釩氧錯合物來作為進行溴化反應的催化劑，探討其催化性質。

ABSTRACT
Mixed-ligand oxovanadium(IV) complexes of 5-nitro-N-salicylidene-phenylalaninato, N-salicylidenephenylalaninato and 3-methoxy-N-salicylidene-phenylalaninato, [VO(sal-D-phe)(L)], [VO(sal-L-phe)(L)] ,[VO(5-NO2-sal-D-phe)(L)], [VO(5-NO2-sal-L-phe)(L)] and [VO(3-CH3O-sal-L-phe)(L)], where L=1,10-phenanthroline, 2,2’-bipyridine, 4,7-dimethyl-1,10-phenanthroline, H2O and ROH, have been synthesized and characterized by elemental analyses and UV/VIS, CD, IR, and EPR spectroscopic measurements.
By using three-dimensional X-ray diffraction methods, the crystal and molecular structures of the following four complexes have been determined:
(1) [VO(sal-D-phe)(OCH3)(HOCH3)]
Orthorhombic, space group P21212, a = 14.3954(4) A, b = 18.9384(7) A, c = 6.7507(2) A, V = 1840.4(1) A3, Z = 4, R = 0.0534, Rw = 0.1075.
(2) [VO(sal-D-phe)(H2O)]
Monoclinic, space group P21, a = 14.3954(4) A, b = 18.9384(7) A, c = 6.7507(2) A,  = 107.897(6)o, V = 795.9(3) A3, Z = 2, R = 0.0536 , Rw = 0.0847.
(3) [VO(sal-L-phe)(OC9H9)(HOC9H9)]
Monoclinic, space group P21, a = 12.7380(1) A, b = 7.9986(2) A, c = 16.1993(3) A,  = 110.6570(6)o, V = 1544.375(3) A3, Z = 2, R = 0.0839 , Rw = 0.1603.
(4) [VO(3-CH3O-sal-L-phe)(4,7-dmphen)](H2O)
Monoclinic, space group P21, a = 6.3312(2) A, b = 20.1158(6) A, c = 11.1132(3) A,  = 98.158(1)o, V = 1403.29(7) A3, Z = 2, R = 0.0694 , Rw = 0.1298.
Based on EPR, UV/VIS and CD spectral data, the [VO(sal-phe)(L)], [VO(5-NO2-sal-phe)(L)] and [VO(3-CH3O-sal-phe)(L)] complexes have distorted octahedral structures in consistence with the X-ray structures. Gaussion analyses of the visible and CD spectra suggest the sequences of the d orbitals for [VO(sal-phe)(OCH3)(HOCH3)]- and [VO(5-NO2-sal-phe)(OCH3)　(HOCH3)]- as dz2＞dyz＞dxz＞dx2-y2＞dxy and for the [VO(sal-phe)(NN)] as dz2＞dyz＞dx2-y2＞dxz＞dxy. The reduction potentials are higher for [VO(sal-phe)(NN)] than for [VO(sal-phe)(OCH3)(HOCH3)]- by about 400 mV, revealing that vanadyl complexes are greatly stabilized by NN ligands.
Preliminary studies on bromination of organic substrates catalyzed by asymmetric vanadyl complexes have been performed.

參考資料：
1. Butler, A.; Carrano, C. J. Coord. Chem. Rev. 1991, 109, 61.
2. Rehder, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 148.
3. Crans, D. C. Comments Inorg. Chem. 1994, 16, 1.
4. Butler, A.; Walker, J. V. Chem. Rev. 1993, 93, 1937.
5. Morningstar, J. E.; Johnson, M. K.; Case, E. E.; Hales, B. J. Biochemistry 1987, 26, 1795.　
6. Schechter, Y.; Karlish, S. J. D. Nature 1980, 284, 556.
7. Mcneill, J. H.; Yuen, V. G.; Hoveyda, H. R.; Orvig. C. J. Med. Chem. 1992, 35, 1489.
8. Crans, D. C.; Mahroof-Tahir, M.; Shin, P. K.; Keramidas, A. D. Mol. Cell. Biochem. 1995, 153, 17.
9. Shechter, Y. Diabetes 1990, 39, 1.
10. Denu, J. M.; Lohse, D. L.; Vijayalakshmi, J.; Saper, M. A.; Dixon, J. E. Proc. Natl. Acad. Sci. USA 1996, 93, 2493.
11. Nakajima, K.; Kojima, K.; Kojuma, M.; Fujita, J. Bull. Chem. Soc. Jpn. 1990, 63, 2620.
12. Nakajima, K.; Kojima, K.; Toriumi, K.; Fujita, J. Bull. Chem. Soc. Jpn. 1989, 62, 760.
13. Bolm, C.; Bienewald, F. Angew. Chem. Int. Ed. Engl. 1995, 34, 2640.
14. Brink, H-B.; Tuynman, A.; Dekker, H-L.; Hemrika, W.;Izumi, Y.; Oshiro, T.; Schoemaker, H-E.; Wever, R. Inorg. Chem. 1998, 37, 6780.
15. Andersson, M.; Willetts, A.; Allenmark, S. J. Org. Chem. 1997, 62, 8455
16. Mimoun, H.; Chaumette, P.; Mignard, M.; Saussine, L.; Nouv. J. De Chim. 1983, 7, 467.
17. K. B. Sharpless, R. C. Michaelson, J. Am. Chem. Soc. 1977, 99, 1990.
18. Schiff, H. Ann. Suppl. 1864, 3, 343
19. Collins, S. R.; Fenton, D. E. Coord. Chem. Rev., 1996, 148, 19.　
20. Clague, M. J.; Keder, N. L.; Butler, A. Inorg. Chem. 1993, 32, 4754.
21. Colpas, G. J.; Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1996, 118, 3469.
22. Hamstra, B. J.;Houseman, A-L. P.; Colpas, G. J.; Kampf, J. W.; LoBrutto, R.; Frasch, W. D.; Pecoraro, V. L. Inorg. Chem. 1997, 36, 4866.
23. Everett, R. R.; Butler, A. Inorg. Chem. 1989, 28, 395.
24. Colpas, G. J.; Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1994, 116, 3627.
25. Chakravarty, J.; dutta, S.; Chakravarty, A. J. Chem. Soc., Commun., 1993, 1091.
26. Zamian, J. R.; Dockal, E. R. Transition Met. Chem. 1996, 21, 370.
27. Cavaco, I.; Pessoa, J. C.; Duarte, M. T.; Henriques, R. T.; Matias, P. M.; Gillard, R. D. J. Chem. Soc., Dalton Trans., 1996, 1989.
28. Cavaco, I.; Pessoa, J. C.; Costa, D.; Duarte, M. T.; Gillard, R. D.; Matias, P. J. Chem. Soc., Dalton Trans., 1994, 149.
29. Pessoa, J. C.; Duarte, M. T.; Gillard, R. D.; Madeira, C.; Matias, P.; Tomaz, I. J. Chem. Soc., Dalton Trans., 1998, 4015.
30. Pessoa, J. C.; Gajda, T.; Gillard, R. D.; Kiss, T.; Luz, S. M.; Moura, J-J. G.; Tomaz, I.; Telo, J. D.; Torok, I. J. Chem. Soc., Dalton Trans., 1998, 3587.
31. Rath, S. P.; Ghosh, T.; Mondal, S. Polyhedron, 1997, 16, 4179.
32. Barral, M. C.; Jimenez-Aparicio, R.; Priego, J. L.; Royer, E. C.; Saucedo, M. J.; Urbanos, F. A. Polyhedron, 1995, 14, 2419.
33. Theriot, L. J.; Carlisle, G. O.; Hu, H. J. J. Inorg. Nucl. Chem. 1969, 31, 3303.
34. Keramidas, A. D.; Papaioannou, A. B.; Vlahos, A.; Kabanos, T. A.; Bonas, G.; Makriyannis, A.; Rapropoulou, C. P.; Terzis, A. Inorg. Chem. 1996, 35, 397.
35. Pessoa, J. C.; Silva, J. A-L.; Vieira, A. L.; Vilas-Boas, L.; O’Brien, P.; Thornton, P. J. Chem. Soc., Dalton Trans., 1992, 1745.
36. Kasahara, R.; Tsuchimoto, M.; Ohba, S.; Nakajima, K.; Ishida, M. Inorg. Chem. 1996, 35, 7661.
37. Dutta, S.; Mondal, S.; Chakravorty, A. Polyhedron, 1995, 14, 1163.
38. Carrano, C. J.; Nuun, C. M.; Quan, R.; Bonadies, J. A.; Pecoraro, V. L. Inorg. Chem. 1990, 29, 944.
39. Mondal, S.; Dutta, S.; Chakravorty, A. J. Chem. Soc., Dalton Trans., 1995, 1115.
40. Duma, T. W.; Hancock, R. D. J. Coord. Chem. 1994, 31, 135.
41. Pasini, A.; Gullotti, M. J. Coord. Chem. 1974, 3, 319.
42. Vergopoulos, V.; Priebsch, W.; Fritzsche, M.; Rehder, D. Inorg. Chem. 1993, 32, 1884.
43. Percy, G. C. J. Inorg. Nucl. Chem. 1975, 32, 2071.
44. Selbin, J.; Holmes, L. H.; McGlynn, S.P.; Inorg. Nucl. Chem. 1963, 25, 1359.
45. Hamilton, D. E. Inorg. Chem. 1991, 30, 1670.
46. Selbin, J. Chem. Rev. 1965, 65, 153.
47. Kolawole, G. A.; Patel, K. S. J. Coord. Chem. 1982, 12, 121.
48. Basu,P.; Pal, S.; Chakravorty, A. J. Chem. Soc., Dalton Trans, 1991, 3217.
49. Hausan, C. R.; Kabanos, T. A.; Keramidas, A. D.; Mentzafos, D.; Terzis, A. Inorg. Chem. 1992, 31, 2857.
50. Cornman, C. R.; Kamrf, J.; Lah, M. S.; Pecoraro, V. L. Inorg. Chem. 1992, 31, 2035.
51. Chakaravorty, J.; Dutta, S.; Chandra, S. K.; Basu, P.; Chakaravorty, A. Inorg. Chem. 1993, 32, 4249.
52. Ballhausen, C. J.; Gray, H. B. Inorg. Chem. 1962, 1, 111.
53. Zah-Letho, J.; Samuel, E.; Livage, J. Inorg. Chem. 1988, 27, 2233.
54. Heinert, D.; Martell, A. E. J. Am. Chem. Soc. 1963, 85, 188.
55. Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706
56. Wang, S. L.; Wang, P. C.; Nieh, Y. P. J. Appl. Cryst. 1990, 52, 23
57. Tang, S-P. W.; Coleman, J. E.; Myer, Y. P. J. Biol. Chem. 1968, 243, 4286.
58. Bosnich, B. J. Am. Chem. Soc. 1968, 90, 627.
59. Stephen F. Mason, “Molecular optical activity and the chiral discrimination”