研究生: |
吳沛凡 |
---|---|
論文名稱: |
含主族元素(Bi、Te)與過渡金屬(Mo、Ru)團簇化合物的合成與化性研究 |
指導教授: | 謝明惠 |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2007 |
畢業學年度: | 95 |
語文別: | 中文 |
論文頁數: | 182 |
中文關鍵詞: | 團簇化合物 |
英文關鍵詞: | Bi, Te, Ru, Mo |
論文種類: | 學術論文 |
相關次數: | 點閱:157 下載:0 |
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1. Bi-Mo-CO系統
將NaBiO3與Mo(CO)6以莫耳比為1:1的比例於MeOC2H4OH中加熱迴流反應,可得到主體結構為四面體的化合物[Bu4N][BiMo3(CO)9(-OC2H4OMe)3Na]。
此化合物可與正一價或正二價陽離子做離子交換反應得到一系列相似結構之產物[BiMo3(CO)9(-OC2H4OMe)3ML]- (ML = Li,Tl,Ca(NCMe)2,Ca(OAc),Pb(NO3),ZnCl,Cd(OAc),HgCl2,CoCl)。有趣的是當[BiMo3(CO)9(-OC2H4OMe)3Na]-加入KCl時卻無法反應,可能是立體障礙造成的結果。此外[BiMo3(CO)9(-OC2H4OMe)3Na]-與Pb(OAc)2反應時則可得到dimer形式的產物。同時我們進一步利用理論計算來佐證實驗中所得到的結果。
2. Te-Ru-CO系統
將K2TeO3與Ru3(CO)12以莫耳比為1:1的比例於MeOH中加熱迴流反應,可得到主體結構為八面體的化合物[PPh4]2[TeRu5(CO)14]•CH2Cl2。利用[PPh4]2[TeRu5(CO)14]•CH2Cl2與CuX (X = Cl,Br,I)反應,依不同比例可生成一系列含銅的新穎化合物:[TeRu5(CO)14CuX]2-、[TeRu5(CO)14Cu2X2]2-、[Te2Ru10(CO)28Cu4X2]2-與[Te2Ru4(CO)10Cu2X2]2-,並探討相互間的轉換關係,此外,我們亦利用理論計算來探討其相關的性質。
1. Bi-Mo-CO system
When NaBiO3 was treated with 1 equiv of Mo(CO)6 in a methanol solution, the novel tetrahedral cluster [BiMo3(CO)9(-OC2H4OMe)3Na]- was formed. [BiMo3(CO)9(-OC2H4OMe)3Na]- was found to undergo ion exchange with cations or dications to give the corresponding clusters [BiMo3(CO)9(-OC2H4OMe)3ML]- (ML = Li, Tl, Ca(NCMe)2, Ca(OAc), Pb(NO3), ZnCl, Cd(OAc), HgCl2, and CoCl). Interestingly, the ion exchange reaction of [BiMo3(CO)9(-OC2H4OMe)3Na]- with KCl was not observed probably due to the size effect, which was further supported by DFT calculations. In addition, further reaction of [BiMo3(CO)9(-OC2H4OMe)3Na]- with Pb(OAc)2 gave the dimeric complex rather than monomer species, which was also demonstrated by DFT calculations.
2. Te-Ru-CO system
The reaction of K2TeO3 with Ru3(CO)12 in a molar ratio of 1: 1 in a methanol solution produced an octahedral cluster [TeRu5(CO)14]2-. When [TeRu5(CO)14]2- was treated with CuX (X = Cl, Br, I) in various ratios, a series of copper-incorporated polynuclear complexes, [TeRu5(CO)14CuX]2-, [TeRu5(CO)14Cu2X2]2-, [Te2Ru10(CO)28Cu4X2]2-, and [Te2Ru4(CO)10Cu2X2]2- were synthesized. The transformation and the nature of these complexes were further studied and compared by DFT calculations.
1. Gates, B. C., Ed. Metal clusters in Catalysis; Amsterdam, 1986.
2. (a) Cotton, F. A.; Adams, R. D.; Cullen, W. R.; Hunter, D. L. Inorg. Chem. 1975, 14, 1395. (b) Whitmire, K. H.; Lagrone, C. B.; Rheingold, A. L. Inorg. Chem. 1986, 25, 2472. (c) Das, B. K.; Kanatzidis, M. G. Polyhedron. 1997, 3061.
3. (a) Curtis, M. D.; Druker, S. H. J. Am. Chem. Soc. 1997, 119, 1027. (b) Sweigart, D. A.; Yu, K.; Li, H.; Watson, E. J.; Virkaitis, K. L.; Carpenter, G. B. Organometallics 2001, 20, 3550.
4. Chérioux, F.; Therrien, B.; Süss-Fink, G. Chem. Commun. 2004, 204.
5. Neumann, R.; Branytska, O. V. J. Org. Chem. 2003, 68, 9510.
6. Limberg, C.; Boggan, S.; Ziemer, B.; Brandt, M. Angew. Chem., Int. Ed. Engl. 2004, 43, 2846.
7. (a) Weller, A. S.; Brayshaw, S. K.; Harrison, A.; McIndoe, J. S.; Marken, F.; Raithby, P. R.; Warren, J. E. J. Am. Chem. Soc. 2007, 129, 1793. (b) Weller, A. S.; Brayshaw, S. K.; Green, J. C.; Hazari, N.; McIndoe, J. S.; Marken, F.; Raithby, P. R. Angew. Chem., Int. Ed. Engl. 2006, 45, 6005.
8. Adams, R. D.; Captain, B.; Smith, M. D.; Beddie, C.; Hall, M. B. J. Am. Chem. Soc. 2007, 129, 5981.
9. Ogo, S.; Kabe, R.; Uehara, K.; Kure, B.; Nishimura, T.; Menon, S. C.; Harada, R.; Fukuzumi, S.; Higuchi, Y.; Ohhara, T.; Tamada, T.; Kuroki, R. Science, 2007, 316, 585.
10. Hinnemann, B.; Nørskov, J. K. J. Am. Chem. Soc. 2003, 125, 1466.
11. (a) Dobbek, H.; Svetlitchnyi, V.; Gremer, L.; Huber, R.; Meyer, O. Science, 2001, 293, 1281. (b) Gourlay, C.; Nielsen, D. J.; White, J. M.; Knottenbelt, S. Z.; Kirk, M. L.; Young, C. G. J. Am. Chem. Soc. 2006, 128, 2164. (c) Panda, R.; Berlinguette, C. P.; Zhang, Y.; Holm, R. H. J. Am. Chem. Soc. 2005, 127, 11092.
12. (a) Chen, L.; Corbet, J. D. J. Am. Chem. Soc. 2003, 125, 1170. (b) Salloum, D.; Gautier, R.; Potel, M.; Gougeon, P. Angew. Chem., Int. Ed. Engl. 2005, 44, 1363.
13. Chitsaz, S.; Fenske, D.; Fuhr, O. Angew. Chem., Int. Ed. Engl. 2006, 45, 8055.
14. Hieber, W.; Gruber, J. Z. Anorg. Allg. Chem. 1958, 296, 91.
15. Xu, Li.; Ugrinov, A.; Sevov, S. C. J. Am. Chem. Soc. 2001, 123, 4091.
16. Grooer, T.; Scheer, M. Organometallics 2000, 19, 3683.
17. Bachman, R. E.; Whitmire, K. H. Inorg. Chem. 1995, 34, 1542.
18. Shieh, M.; Mia, F.-D.; Peng, S.-M.; Lee, G.-H. Inorg. Chem. 1993, 32, 2785.
19. McNeese, T. J.; Cohen, M. B.; Foxman, B. M. Organometallics 1984, 3, 552.
20. Shieh, M.; Cherng, J.-J.; Lee, G.-H.; Peng, S.-M.; Ueng, C.-H. Organometallics 2000, 19, 213.
21. Shieh, M.; Cherng, J.-J.; Lai, Y.-W.; Ueng, C.-H.; Peng, S.-M.; Liu, Y.-H. Chem. Eur. J. 2002, 8, 4522.
22. 郭可欣,國立台灣師範大學碩士論文,2001。
23. van Hal, J. W.; Whitmire, K. H.; Zouchoune, B.; Halet, J.-F.; Saillard, J.-Y. Inorg. Chem. 1995, 34, 5455.
24. Shriver, D. F.; Drezdzon, M. A. The Manpulation of Air-Sensitive Compound; Wiley: New York, 1986.
25. 張簡宗德,國立台灣師範大學碩士論文,2004。
26. 蔡宛珍,國立台灣師範大學碩士論文,2006。
27. 詹莉芬,國立台灣師範大學碩士論文,1997。
28. 謝明惠,賴韻文,未發表之結果。
29. Sheldrick G. M., SHELXL97, University of Göttingen, Germany, 1997.
30. 謝明惠,陳輝龍,未發表之結果。
31. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gill, P. M. W.; Challacombe, M.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian: Wallingford, CT USA, 2004.
32. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Becke, A. D. J. Chem. Phys. 1992, 96, 2155. (c) Becke, A. D. J. Chem. Phys. 1992, 97, 9173.
33. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785.
34. (a) Schwerdtfeger, P.; Dolg M.; Schwarz, W. H.; Bowmaker, G. A.; Boyd, P. D. W. J. Chem. Phys. 1989, 91, 1762. (b) Andrae, D.; Haubermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123. (c) Bergner, A.; Dolg M.; KŸchle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431.
35. Dunning, T. H., Jr.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer H. F., III, Ed.; Plenum: New York, 1976; Vol. 3, p 1.
36. (a) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1983, 78, 4066. (b) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.
37. Wiberg, K. B. Tetrahedron 1968, 24, 1083. The Wiberg bond indices (bond orders) are a measure of bond strength.
38. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
39. Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
40. 謝明惠,繆佳曄,未發表之結果。
41. Manos, M. J.; Chrissafis, K.; Kanatzidis M. G. J. Am. Chem. Soc. 2006, 128, 8875.
42. Shannon, R. D. Acta Crystallogr. 1976, A32, 751.
43. Yue, Y-F.; Wang, B-W.; Gao, E-Q.; Fang, C-J.; He, C.; Yan, C-H. Chem. Commun., 2007, 2034.
44. Arnold, P. L.; Liddle, S. T.; Mcmaster, J.; Jones, C.; Mills, D. P. J. Am. Chem. Soc. 2007, 129, 5360.
45. Hull, K. L.; Noll, B. C.; Henderson, K. W. Organometallics 2006, 25, 4072.
46. Luo, Q.; Zhang, X. H.; Huang, K. L.; Liu, S. Q.; Yu, Z. H.; Li, Q. S. J. Phys. Chem. A 2007, 111, 2930.
47. Montoya, A.; Schlunke, A.; Haynes, B. S. J. Phys. Chem. B 2006, 110, 17145.
48. (a) Jansen, H. B.; Ross, P. Chem. Phys. Lett. 1969, 3, 140. (b) Boys, S. B.; Bernardi, F. Mol. Phys. 1970, 19, 533. (c) Mayer, I.; Surjan, P. R. Chem. Phys. Lett. 1992, 191, 497. (d) Simon, S.; Duran, M.; Dannenberg, J. J. J. Chem. Phys. 1996, 105, 11024. (e) Salvador, P.; Paizs, B.; Duran, M.; Suhai, S. J. Comput. Chem. 2001, 22, 76.
49. 勞工安全衛生簡訊第58期-鉈的特性與健康危害。
50. Wiles, A. B.; Pike, R. D. Organometallics 2006, 25, 3282.
51. Chandrasekaran, P.; Maque, J. T.; Balakrishna, M. S. Inorg. Chem. 2006, 45, 6678.
52. 李長儒,國立台灣師範大學碩士論文,2003。
53. 陳鴻文,國立台灣師範大學碩士論文,2004。
54. 朱緯廷,國立台灣師範大學碩士論文,2006。
55. Parr, R. G.; Yang, W. J. Am. Chem. Soc. 1984, 106, 4049.
56. 朱晏頤,國立台灣師範大學碩士論文,2007。