研究生: |
林怡君 |
---|---|
論文名稱: |
含硒之鉻、鉬、鎢金屬及碲之鉻金屬羰基化合物的合成及反應性研究 |
指導教授: |
謝明惠
Shieh, Ming-Huey |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2003 |
畢業學年度: | 91 |
語文別: | 中文 |
論文頁數: | 126 |
中文關鍵詞: | 金屬團簇化合物 、固氮酵素 |
英文關鍵詞: | metal clusters, nitrogenase |
論文種類: | 學術論文 |
相關次數: | 點閱:170 下載:0 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
[1] 硒(Se)-鉻(Cr)、鉬(Mo)、鎢(W)的研究
將 [Se2Cr3(CO)10]2- 與1當量的W(CO)6在丙酮中加熱反應,可得混合鉻鎢金屬的化合物 [Se2Cr2W(CO)10]2-;若以過量的W(CO)6在丙酮中加熱反應,則可得開放結構化合物 [Se2W4(CO)18]2- 及雙三角錐封閉結構化合物 [Se2W3(CO)10]2-。
[Se2Cr3(CO)10]2- 與第七族的異核金屬 Mn(CO)5Br反應:在丙酮中反應,可得一結構特殊的混合鉻-錳金屬化合物 [Me2CSe2Cr2Mn(CO)14]-。
[Se2Mo3(CO)10]2- 與第八族的異核金屬Fe(CO)5於丙酮中反應,可得到具有cubic結構的化合物 [Se3Mo5(CO)9(=O){C(CH3)2CH2C(=O)CH3}]3-(主產物)和已知產物[SeFe3(CO)9]2-(副產物);與Ru3(CO)12反應則得到已知產物具八面體結構的化合物 [Se2Ru4(m-CO)4(CO)8]2-。[Se2W3(CO)10]2- 與第八族的異核金屬Fe(CO)5反應則得到已知產物 [SeFe3(CO)9]2-。
[2] 碲(Te)-鉻(Cr)系統的研究
將Te與Cr(CO)6以1:3的比例在鹼性甲醇溶液中反應,再加入Et4NBr則可得黃褐色化合物 [Et4N]2[Te{Cr(CO)5}3]。不同於 [Te{Cr(CO)5}2]2-,此產物於MeOH溶液中可穩定存在。
[Te{Cr(CO)5}2]2- 與第八族的異核金屬Fe(CO)5、Ru3(CO)12反應,皆得到氧化性產物 [Te{Cr(CO)5}3]2-,而在與Ru3(CO)12的反應,另外可得一具四面體結構之化合物 [TeRu3(CO)9]2-。[Te{Cr(CO)5}2]2- 與HBF4反應可生成一質子化產物 [HTe{Cr(CO)5}2]-;於CH3CN溶液中加熱,則可得到一乙基化產物 [EtTe{Cr(CO)5}2]-;另外與Cr(CO)6反應,則成功合成出 [Te{Cr(CO)5}3]2-。
[1] Se-Cr system
Refluxing [Se2Cr3(CO)10]2- with 1 equiv. of W(CO)6 in acetone yields the W-substituted dichromium cluster [Se2Cr2W(CO)10]2-. On the other hand, refluxing [Se2Cr3(CO)10]2- with excess W(CO)6 in acetone leads to formation of the arachno-cluster [Se2W4(CO)18]2- and the closo-cluster [Se2W3(CO)10]2-. When [Se2Cr3(CO)10]2- was treated with Mn(CO)5Br in acetone at room temperature, the unusual mixed-metal cluster [Me2CSe2Cr2Mn(CO)14]- was produced.
Reaction of [Se2Mo3(CO)10]2- with Fe(CO)5/KOH forms the cubane-like cluster [Se3Mo5(CO)9(=O){C(CH3)2CH2C(=O)CH3}]3- and the known compound [SeFe3(CO)9]2-. While treatment with Ru3(CO)12 produces the known octahedral complex [Se2Ru4(m-CO)4(CO)8]2-, the reaction of [Se2W3(CO)10]2- with Fe(CO)5/KOH yields the known compound [SeFe3(CO)9]2-.
[2] Te-Cr system
Reaction of Te powder with Cr(CO)6 in a molar ratio of 1:3 in basic methanol solution produces [Et4N]2[Te{Cr(CO)5}3] by the addition of Et4NBr. Unlike [Te{Cr(CO)5}2]2-, this species is stable in methanol solution at room temperature.
Whereas [Te{Cr(CO)5}2]2- was treated with Fe(CO)5 to form [Te{Cr(CO)5}3]2-, the treatment with Ru3(CO)12 affords [Te{Cr(CO)5}3]2- and the tetrahedral cluster [TeRu3(CO)9]2-. [Te{Cr(CO)5}2]2- can further be protonated with HBF4 to form the monohydrido complex [HTe{Cr(CO)5}2]-. Interestingly, [Te{Cr(CO)5}2]2- in refluxing CH3CN leads to ethylated complex [EtTe{Cr(CO)5}2]-. In addition, the reaction of [Te{Cr(CO)5}2]2- with Cr(CO)6 gives the oxidizing product [Te{Cr(CO)5}3]2-.
1. (a) Adams, R. D.; Captain, B.; Fu, W. Inorg. Chem. 2003, 42, 1328.
(b) Adams, R. D.; Captain, B.; Fu, W.; Smith, M. D. Inorg. Chem. 2002, 41, 5593. (c) Adams, R. D.; Captain, B.; Fu, W. Organometallics 2000, 19, 3670.
2. Alexeev, O. S.; Gates, B. C. Ind. Eng. Chem. Res. 2003, 42, 1571.
3. Haak, S.; Neels, A.; Stœckli-Evans, H.; Süss-Fink, G.; Thomas, C. M. Chem. Commun. 1999, 1959.
4. Shimada, T.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 6646.
5. Coucouvanis, D.; Han, J.; Moon, N. J. Am. Chem. Soc. 2002, 124, 216.
6. Adams, H.; Gill, L. J.; Morris, M. J. Organometallics 1996, 15, 464.
7. Chi, Y.; Peng, S.-M.; Lee, G.-H.; Su, C.-J. Organometallics 2001, 20, 1102.
8. Shieh, M.; Cherng, J.-J.; Lai, Y.-W.; Ueng, C.-H.; Peng, S.-M.; Liu, Y.-H. Chem. Eur. J. 2002, 8, 4522.
9. Wilkinson, G.; Stone, F. G. A.; Abel, E. W. Comprehensive Organometallic Chemistry; Pergamon: Oxford, 1982.
10. Schmid, G. Angew. Chem., Int. Ed. Engl. 1978, 17, 392.
11. Abel, E. W.; Stone, F. G. A.; Wilkinson, G. Comprehensive Organometallic Chemistry II; Elsevier Science Inc.: New York, 1995, Vol. 5.
12. Sekar, P.; Ibers, J. A. Inorg. Chem. 2002, 41, 450.
13. Shieh, M.; Ho, L.-F.; Jang, L.-F.; Ueng, C.-H.; Peng, S.-M.; Liu, Y.-H. Chem. Commun. 2001, 1014.
14. Collins, M. J.; Gillespie, R. J.; Kolis, J. W.; Sawyer, J. F. Inorg. Chem. 1986, 25, 2057.
15. Kanatzidis, M. G.; Das, B. K. Inorg. Chem. 1995, 34, 5721.
16. Hieber, W.; Gruber, J. Z. Anorg. Allg. Chem. 1958, 296, 91.
17. Shieh, M.; Liou, Y.; Hsu, M.-H.; Chen, R.-T.; Yeh, S.-J.; Peng, S.-M.; Lee, G.-H. Angew. Chem., Int. Ed. Engl. 2002, 41, 2384.
18. Shieh, M.; Chen, H.-S.; Yang, H.-Y.; Lin, S.-F.; Ueng, C.-H. Chem. Eur. J. 2001, 7, 3152.
19. Shieh, M.; Shieh, M.-H.; Tsai, Y.-C; Ueng, C.-H. Inorg. Chem. 1995, 34, 5088.
20. 吳美芬,台灣師範大學碩士論文,2001,頁107.
21. Darensbourg, D. J.; Zalewski, D. J.; Sanchez, K. M.; Delord, T. Inorg. Chem. 1988, 27, 821.
22. Kolis, J. W.; Roof, L. C.; Pennington, W. T. Inorg. Chem. 1992, 31, 2056.
23. 何莉芳,台灣師範大學碩士論文,2000.
24. 林淑芬,台灣師範大學碩士論文,2001.
25. Goh, L. Y. Coord. Chem. Rev. 1999, 185-186, 257.
26. 詹莉芬,台灣師範大學碩士論文,1997.
27. Rohrmauu, J.; Herrmann, W. A. J. Organomet. Chem. 1984, 273, 221.
28. Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-Sensitive
Compounds; Wiley: New York, 1986.
29. (a) Huang, K.-C.; Tsai, Y.-C.; Lee, G.-H.; Peng, S.-M.; Shieh, M. Inorg. Chem. 1997, 36, 4421. (b) 蔡易州,台灣師範大學碩士論文,1994.
30. Shieh, M.; Tsai, Y.-C. Inorg. Chem. 1994, 33, 2303.
31. Bachman, R. E.; Whitmire, K. H. Inorg. Chem. 1994, 33, 2527.
32. 紀信宏,台灣師範大學碩士論文,2001.
33. 郭玉雯,未發表結果。
34. Tate, D. P.; Knipple, W. R.; Augl, J. M. Inorg. Chem. 1962, 1, 433.
35. Gordon, A. J.; Ford, R. A. The Chemist’s Compasion; Wiely: New York, 1972; p445.
36. Whitmire, K. H.; Xu, L. Organometallics 2002, 21, 2581.
37. Thöne, C.; Jones, P. G. Inorg. Chem. 1996, 35, 6625.
38. Thöne, C.; Jones, P. G.; Laube, J. Eur. J. Inorg. Chem. 1998, 397.
39. Belin, C.; Makani, T.; Rozière, J. J. Chem. Soc., Chem. Commum. 1985, 118.
40. Angelici, R. G.; Gingerich, R. G. W. J. Am. Chem. Soc. 1979, 101, 5604.
41. Angelici, R. G.; Gingerich, R. G. W. Organometallics 1983, 2, 89.
42. Arndtsen, B. A.; Bergman, R. G. J. Organomet. Chem. 1995, 504, 143.
43. Averill, B. A.; Eldredge, P. A.; Bose, K. S.; Barber, D. E.; Bryan, R. F.; Sinn, E.; Rheigold, A. Inorg. Chem. 1991, 30, 2365.
44. Han, J.; Koutmos, M.; Ahmad, S. A.; Coucouvanis, D. Inorg. Chem. 2001, 40, 5985.
45. Weng, Z.; Leong, W. K.; Vittal, J. J.; Goh, L. Y. Organometallics 2003, 22, 1645.
46. Hernández-Molina, R.; Sykes, A. G. J. Chem. Soc., Dalton Trans. 1999, 3137.
47. Mathur, P.; Chakrabarty, D.; Hossain, M. M.; Rashid, R. S.; Rugmini,V.; Rheingold, A. L. Inorg. Chem. 1992, 31, 1106.
48. Mathur, P.; Bhunia, A. K.; Kumar, A.; Chatterjee, S; Mobin, S. M. Organometallics 2002, 21, 2215.
49. Hernández-Molina, R.; Sokolov, M. N.; Sykes, A. G. Acc. Chem. Res. 2001, 34, 223.
50. Tatsumi, K.; Hong, M.; Cao, R.; Kawaguchi, H. Inorg. Chem. 2002, 41, 4824.
51. Stauf, S.; Reisner, C.; Tremel, W. Chem. Commum. 1996, 1749.
52. Brandl, M.; Brunner, H.; Wachter, J.; Zabel M. Organometallics 2002, 21, 3069.
53. Brunner, H.; Stückl, A. C.; Wachter, J.; Wanninger, R.; Zabel, M. Angew. Chem., Int. Ed. Engl. 2001, 40, 2463.
54. 游宗憲,台灣師範大學碩士論文,2001,頁30.
55. Vaira, M. D.; Peruzzini, M.; Stoppioni, P. Inorg. Chem. 1991, 30, 1001.
56. 賴韻文,未發表結果。
57. Curtis, M. D.; Han, K. R.; Butler, W. M. Inorg. Chem. 1980, 19, 2096.
58. Curtis, M. D.; Klingler, R. J.; Butler, W. M. J. Am. Chem. Soc. 1978, 100, 5034.
59. Douglas, B. E.; McDaniel, D. H.; Alexander, J. J. Concepts and Models of Inorganic Chemistry; John Wiley & Sons, Inc: New York, 3rd edn., 1994.
60. Ibers, J. A.; Wardle, R. W. M.; Bhaduri, S.; Chau, C.-N. Inorg. Chem. 1988, 27, 1747.
61. Rupp, E.; Nowak, F.; Fiechter, S.; Reck, G.; Eyert, V.; Alonso-Vante, N.; Tributsch, H. Eur. J. Inorg. Chem. 2001, 2489.
62. Choi, D. S.; Hong, S. H.; Lee, S. S.; Chung, Y. K. J. Organomet. Chem. 1999, 579, 385.
63. Huang, K.-C.; Shieh, M.-H.; Jang, R.-J.; Peng, S.-M.; Lee,G.-H.; Shieh, M. Organometallics 1998, 17, 5202.
64. Rottinger, E.; Vahrenkamp, H. J. Organomet. Chem. 1981, 213, 1.
65. Ogino, H.; Inomata, S.; Tobita, H. Chem. Rev. 1998, 98, 2093.
66. Mathur, P.; Mukhopadhyay, S.; Ahmed, M. O.; Lahiri, G. K.; Chakraborty, S.; Walawalkar, M. G. Organometallics 2000, 19, 5787.
67. Mathur, P.; Mukhopadhyay, S.; Lahiri, G. K.; Chakraborty, S.; Thöne, C. Organometallics 2002, 21, 5209.
68. Mathur, P.; Ghose, S.; Hossain, M. M.; Hitchcock, P. B.; Nixon, J. F. J. Organomet. Chem. 1997, 542, 265.
69. Mathur, P.; Ghose, S.; Hossain, M. M.; Vahrenkamp, H. J. Organomet. Chem. 1997, 538, 185.