研究生: |
曾宜秀 |
---|---|
論文名稱: |
碳-氫鍵活化合成錸金屬環錯合物及其分子辨識研究 Preparation of Rhenium-Based Metallacycles via C-H Bond Activation and Their Molecular Recognition Capabilities |
指導教授: |
許貫中
Hsu, Kung-Chung 呂光烈 Lu, Kuang-Lieh |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 160 |
中文關鍵詞: | 金屬環錯合物 、錸 、晶體結構 、分子辨識 、碳-氫鍵活化 |
英文關鍵詞: | metallacycle, rhenium, crystal structure, molecular recognition |
論文種類: | 學術論文 |
相關次數: | 點閱:204 下載:2 |
分享至: |
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本論文的研究是利用Re2(CO)10與2-(2-pyridyl)-benzimidazole (HBim-C6H4N)
及1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1)、
α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2) 、
1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3) 、
1,2-bis(4-pyridyl)ethane (bpea, L4)或1,3-bis(4-pyridyl)propane (bppa, L5)等有機配
子在水熱條件下自組裝合成,分別得到[{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1)、
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3)、
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)等錸
金屬錯合物。錯合物15經由UV-vis、IR、NMR、FAB-MS等方法鑑定,其結構
也以單晶X光繞射法解析。化合物1為一雙核非環狀錯合物,具發光特性,可藉
由可見-紫外光光譜上的差異來辨識Hg+、Cu2+及Ag+等三種金屬離子。化合物25
的結構為雙核金屬環化物,除了其光物理性質之外,該系列分子的特色是錸金屬
將有機配子2-(2-pyridyl)benzimidazole中3號位置(C3)的碳-氫鍵活化而形成雙核
環化物。
Compounds [{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1),
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2), [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3),
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4), and [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)
were successfully synthesized by treatment of Re2(CO)10 with
2-(2-pyridyl)-benzimidazole (HBim-C6H4N) and
1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1),
α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2),
1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3),
1,2-bis(4-pyridyl)ethane (bpea, L4), or 1,3-bis(4-pyridyl)propane (bppa, L5)
respectively, under solvothermal conditions. The series of rhenium-based complexes
15 was characterized using IR, UV-vis, and NMR spectroscopic techniques. The
structures were further confirmed by X-ray single-crystal diffraction analysis.
Compound 1 is a dimetallic complex with an acyclic conformation. Compound 1
exhibited luminescent properties. In addition, it recognized Hg+,Cu2+ and Ag+ ions
by means of discrimination on UV-vis spectra. Crystal structures showed that
compounds 25 possess dimetallic cyclic conformations. It is noteworthy that C-H
activation on 2-(2-pyridyl)benzimidazole occurred during preparation of these
metallacyclic compounds.
1. (a) Lehn, J. M. Supramolecular Chemistry, Concepts and Perspecti Ves;VCH:
Weinheim, 1995. (b) Leininger, S.; Olenyuk, B.; Stang, P. J . Chem. Rev. 2000,
100, 853. (c) Jones, C. J. Chem. Soc. Rev. 1998, 27, 289. (d) Swiegers, G. F.;
Malefetse, T. J. Chem. Rev. 2000, 100, 3483. (e) Fujita, M.; Umemoto, K.;
Yoshizawa, M.; Fujita, N.; Kusukawa, T.; Biradha, K. Chem. Commun. 2001,
509. (f) Sauvage, J.-P. Acc. Chem. Res. 1998, 31, 611. (g) Holliday, B. J.; Mirkin,
C. A. Angew. Chem. Int. Ed. 2001, 40, 2022. (h) Cotton, F. A.; Lin, C.; Murillo,
C. A. Acc. Chem. Res. 2001, 34, 759. (i) Caulder, D. L.; Raymond, K. N. Acc.
Chem. Res. 1999, 32, 975. (j) Ruben, M.; Rojo, J.; Romero -Salguero, F. J.;
Uppadine, L. H.; Lehn, J. M. Angew. Chem., Int. Ed. 2004, 43, 3644. (k) Severin,
K. Coord. Chem. Rev. 2003, 245, 3. (l) Navarro, J. A. R.; Lippert, B. Coord.
Chem. Rev. 1999, 185, 653. (m) Albrecht, M.; Janser, I.; Frohlich, R. Chem.
Commun. 2005, 157.
2. (a) Gianneschi, N. C.; Masar, M. S.; Mirkin, C. A. Acc. Chem. Res. 2005, 38,
825. (b) Kovbasyuk, L.; Kramer, R. Chem. Rev. 2004, 104, 3161. (c) Sanders, J.
K. M. Chem. Eur. J. 1998, 4, 1378. (d) Hof, F.; Rebek, J. Proc. Natl. Acad. Sci.
U.S.A. 2002, 99, 4775. (e) Vriezema, D. M.; Aragones, M. C.; Elemans, J. A. A.
W.; Cornelissen, J. J. L. M.; Rowan, A. E.; Nolte, R. J. M. Chem. Rev. 2005, 105,
1445. (f) Yoshizawa, M.; Tamura, M.; Fujita, M. Science 2006, 312, 251. (g)
Amijs, C. H. M.; van Klink, G. P. M.; van Koten, G. Dalton Trans. 2006, 308.
3. (a) Thanasekaran, P.; Liao, R. T.; Liu, Y. H.; Rajendran, T.; Rajagopal, S.; Lu,
K. L. Coord. Chem. Rev. 2005, 249, 1085. (c) Dinolfo, P. H.; Hupp, J. T. Chem.
Mater. 2001, 13, 3113. (b) Sun, S. S.; Lees, A. J. Coord. Chem. Rev. 2002, 230,
171. (d) Slone, R. V.; Benkstein, K. D.; Belanger, S.; Hupp, J. T.; Guzei, I. A.;
72
Rheingold, A. L. Coord. Chem. Rev. 1998, 171, 221. (e) Woessner, S. M.; Helms,
J. B.; Shen, Y.; Sullivan, B. P. Inorg. Chem. 998, 37, 5406. (f) Lee, S. J.; Lin, W.
J. Am. Chem. Soc. 2002, 124, 4554. (g) Sun, S. S.; Lees, A. J. Chem. Commun.
2001, 103.
4. (a) Schmittel, M.; Lin, H.-W. Angew. Chem., Int. Ed. 2007, 46, 893 (b) Yoon, S.;
Miller, E. W.; He, Q.; Do, P. H.; Chang, C. J. Angew. Chem. Int. Ed. 2007, 46,
6658 (c) Huang, C.-C.; Yang, Z.; Lee, K.-H.; Chang, H.-T. Angew. Chem. Int. Ed.
2007, 46, 6824 (d) Komatsu, K.; Urano, Y.; Kojima, H.; Nagano, T. J. Am. Chem.
Soc. 2007, 129, 13447 (e) Ha-Thi, M.-H.; Penhoat, M.; Michelet, V.; Leray, I.
Org. Lett. 2007, 9, 1133 (f) Batista, R. M. F.; Oliveira, E.; Costa, S. P. G.; Lodeiro,
C.; Raposo, M. M. M. Org. Lett. 2007, 9, 3201 (g) Ray, D.; Bharadwaj, P. K.
Inorg. Chem. 2008, 47, 2252.
5. (a) Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Acc. Chem. Res. 2005, 38,
371 (b) Takaoka, K.; Kawano, M.; Hozumi, T.; Ohkoshi, S.-I.; Fujita, M. Inorg.
Chem. 2006, 45, 3976 (c) Yoshizawa, M.; Kusukawa, T.; Kawano, M.; Ohhara, T.;
Tanaka, I.; Kurihara, K.; Niimura, N.; Fujita, M. J. Am. Chem. Soc. 2005, 127,
2798 (d) Tashiro, S.; Tominaga, M.; Kawano, M.; Therrien, B.; Ozeki, T.; Fujita,
M. J. Am. Chem. Soc. 2005, 127, 4546 (e) Yoshizawa, M.; Ono, K.; Kumazawa,
K.; Kato, T.; Fujita, M. J. Am. Chem. Soc. 2005, 127, 10800 (f) Tominaga, M.;
Suzuki, K.; Murase, T.; Fujita, M. J. Am. Chem. Soc. 2005, 127, 11950.
6. (a) Fujita, K.-I.; Yamashita, M.; Puschmann, F.; Alvarez-Falcon, M. M.;
Incarvito, C. D.; Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 9044 (b) Yamashita,
K.-I.; Kawano, M.; Fujita, M. J. Am. Chem. Soc. 2007, 129, 1850 (c) Kamiya, N.;
Tominaga, M.; Sato, S.; Fujita, M. J. Am. Chem. Soc. 2007, 129, 3816 (d)
Nishioka, Y.; Yamaguchi, T.; Yoshizawa, M.; Fujita, M. J. Am. Chem. Soc. 2007,
129, 7000 (e) Suzuki, K.; Kawano, M.; Sato, S.; Fujita, M. J. Am. Chem. Soc.
73
2007, 129, 10652 (f) Yamauchi, Y.; Yoshizawa, M.; Fujita, M. J. Am. Chem. Soc.
2008, 130, 5832.
7. (a) Kaim, W.; Schwederski, B.; Dogan, A.; Fiedler, J.; Kuehl, C. J.; Stang, P. J.
Inorg. Chem. 2002, 41, 4025 (b) Zheng, Y.-R.; Yang, H.-B.; Northrop, B. H.;
Ghosh, K.; Stang, P. J. Inorg. Chem. ASAP (c) Deak, A.; Megyes, T.; Tarkanyi,
G.; Kiraly, P.; Biczok, L.; Palinkas, G.; Stang, P. J. J. Am. Chem. Soc. 2006, 128,
12668 (d) Yang, H.-B.; Ghosh, K.; Northrop, B. H.; Zheng, Y.-R.; Lyndon, M. M.;
Muddiman, D. C.; Stang, P. J. J. Am. Chem. Soc. 2007, 129, 14187 (e) Kuehl, C.
J.; Huang, S. D.; Stang, P. J. J. Am. Chem. Soc. 2001, 123, 9634 (f) Yang, H.-B.;
Ghosh, K.; Zhao, Y.; Northrop, B. H.; Lyndon, M. M.; Muddiman, D. C.; White,
H. S.; Stang, P. J. J. Am. Chem. Soc. 2008, 130, 839 (g) Li, S.-S.; Yan, H.-J.; Wan,
L.-J.; Yang, H.-B.; Northrop, B. H.; Stang, P. J. J. Am. Chem. Soc. 2007, 129,
9268 (h) Jude, H.; Sinclair, D. J.; Das, N.; Sherburn, M. S.; Stang, P. J. J. Org.
Chem. 2006, 71, 4155 (i) Chi, K.-W.; Addicott, C.; Moon, M.-E.; Lee, H. J.; Yoon,
S. C.; Stang, P. J. J. Org. Chem. 2006, 71, 6662 (j) Huang, F.; Yang, H.-B.; Das,
N.; Maran, U.; Arif, A. M.; Gibson, H. W.; Stang, P. J. J. Org. Chem. 2006, 71,
6623 (k) Yang, H.-B.; Ghosh, K.; Arif, A. M.; Stang, P. J. J. Org. Chem. 2006, 71,
9464 (l) Yang, H.-B.; Das, N.; F. H.; Hawkridge, A. M.; Dz, D. D.; Arif, A. M.;
Finn, M. G.; Muddiman, D. C.; Stang, P. J. J. Org. Chem. 2006, 71, 6644 (m)
Northrop, B. H.; Glockner, A.; Stang, P. J. J. Org. Chem. 2008, 73, 1787 (n) Das,
N.; Ghosh, A.; Singh, O. M.; Stang, P. J. Org. Lett. 2006, 8, 1701 (o) Yang, H.-B.;
Ghosh, K.; Northrop, B. H.; Stang, P. J. Org. Lett. 2007, 9, 1561 (p) Yang, H.-B.;
Ghosh, K.; Das, N.; Stang, P. J. Org. Lett. 2006, 8, 3991 .
8. (a) Dixon, F. M.; Eisenberg, A. H.; Farrell, J. R.; Mirkin, C. A. Inorg. Chem.
2000, 39, 3432 (b) Liu, X.; Eisenberg, A. H.; Stern, C. L.; Mirkin, C. A. Inorg.
Chem. 2001, 40, 2940 (c) Gianneschi, N. C.; Mirkin, C. A. Inorg. Chem. 2002, 41,
74
5326 (d) Masar, M. S.; Mirkin, C. A.; Stern, C. L.; Zakharov, L. N.; Rheingold, A.
L. Inorg. Chem. 2004, 43, 4693 (e) Holliday, B. J.; Farrell, J. R.; Mirkin, C. A. J.
Am. Chem. Soc. 1999, 121, 6316 (f) Jeon, Y.-M.; Heo, J.; Brown, A. M.; Mirkin,
C. A. Organometallics 2006, 25, 2729 (g) Brown, A. M.; Ovchinnikov, M. V.;
Stern, C. L.; Mirkin, C. A. J. Am. Chem. Soc. 2004, 126, 14316 (h) Gianneschi, N.
C.; Nguyen, S. T.; Mirkin, C. A. J. Am. Chem. Soc. 2005, 127, 1644 (i) Yoon, H.
J.; Heo, J.; Mirkin, C. A. J. Am. Chem. Soc. 2007, 129, 14182 (j) Holliday, B. J.;
Arnold, F. P.; Mirkin, C. A. J. Phys. Chem. A 2003, 107, 2737 (k) Eisenberg, A.
H.; Dixon, F. M.; Mirkin, C. A.; Stern, C. L.; Incarvito, C. D.; Rheingold, A. L.
Organometallics 2001, 20, 2052.
9. Yang, H.-B.; Hawkridge, A. M.; Huang, S. D.; Das, N.; Bunge, S. D.; Muddiman,
D. C.; Stang, P. J. J. Am. Chem. Soc. 2007, 129, 2120.
10. Ghosh, K.; Yang, H.-B.; Northrop, B. H.; Lyndon, M. M.; Zheng, Y.-R.;
Muddiman, D. C.; Stang, P. J. J. Am. Chem. Soc. 2008, 130, 5320.
11. Suzuki, K.; Kawano, M.; Sato, S.; Fujita, M. J. Am. Chem. Soc. 2007, 129, 10652.
12. Yamashita, K.-I.; Kawano, M.; Fujita, M. J. Am. Chem. Soc. 2007, 129, 1850.
13. Kawano, M.; Kawamichi, T.; Haneda, T.; Kojima, T.; Fujita, M. J. Am. Chem. Soc.
2007, 129, 15418.
14. Khoshbin, M. S.; Ovchinnikov, M. V.; Mirkin, C. A.; Zakharov, L. N.; Rheingold,
A. L. Inorg. Chem. 2005. 44, 496.
15. Farha, O. K.; Spokoyny, A. M.; Mulfort, K. L.; Hawthorne, M. F.; Mirkin, C. A.;
Hupp, J. T. J. Am. Chem. Soc. 2007, 129, 12680.
16. (a) Slone, R. V.; Benkstein, K. D.; langer, S. B.; Hupp, J. T.; Guzei, I. A.;
Rheingold, A. L. Coord. Chem. Rev. 1998, 171, 221. (b) Benkstein, K. D.;
Hupp, J. T.; Stern, C. L. Inorg. Chem. 1998, 37, 5404.
75
17. Dinolfo, P. H.; Coropceanu, V.; Bredas, J.-L.; Hupp, J. T. J. Am. Chem. Soc.
2006, 128, 12592.
18. (a) Rajendran, T.; Manimaran, B.; Lee, F.-Y.; Lee, G.-H.; Peng, S.-M.; Wang, C.
M.; Lu, K.-L. Inorg. Chem. 2000, 39, 2016 (b) Rajendran, T.; Manimaran, B.;
Liao, R.-T.; Lin, R.-J.; Thanasekaran, P.; Lee, G.-H.; Peng, S.-M.; Liu, Y.-H.;
Chang, I.-J.; Rajagopal, S.; Lu, K.-L. Inorg. Chem. 2003, 42, 6388.
19. Manimaran, B.; Rajendran, T.; Lu, Y.-L.; Lee, G.-H.; Peng, S.-M.; Lu, K.-L. J.
Chem. Soc., Dalton Trans. 2001, 515.
20. Sathiyendiran, M.; Liao, R.-T.; Thanasekaran, P.; Luo, T.-T.; Venkataramanan, N.
S.; Lee, G.-H.; Peng, S.-M.; Lu, K.-L. Inorg. Chem. 2006, 45, 10052
21. Liao, R.-T.; Yang, W.-C.; Thanasekaran, P.; Tsai, C.-C.; Sathiyendiran, M.; Liu,
Y.-H.; Rajendran, T.; Lin, H.-M.; Tseng, T.-W.; Lu, K.-L., Chem. Commun. 2008,
Accepted
22. Dugas H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action;
Springer, 1996.
23. http://www.chemedu.ch.ntu.edu.tw/lecture/molecular/2.htm
24. (a) Swager, T. M. Acc. Chem. Res. 1998, 31,201 (b) Valeur, B.; Leray I. Coord.
Chem. Rev. 2000, 205, 3.
25. Resendiz, M. J. E.; Noveron, J. C.; Disteldorf, H.; Fischer, S.; Stang, P. J. Org.
Lett. 2004, 6, 651.
26. Ha-Thi, M.-H.; Michelet, M. P. V.; Leray, I. Org. Lett. 2007, 9, 1133.
27. Batista, R. M. F.; Oliveira, E.; Costa, S. P. G.; Lodeiro, C.; Raposo, M. M. M.
Org. Lett. 2007 , 9, 3201.
28. Sathiyendiran, M.; Chang, C.-H.; Chuang, C.-H.; Luo, T.-T.; Wen, Y.-S.; Lu,
K.-L. Dalton Trans. 2007, 1872.
29. Su, C.-Y.; Cai, Y.-P.; Chen, C.-L.; Smith, M. D.; Kaim W.; zur Loye, H.-C.; J.
76
Am. Chem. Soc. 2003, 125, 8595.
30. Shi, Z.; Thummel, R. P. J. Org. Chem. 1995, 60, 5935
31. Dinolfo, P. H.; Benkstein, K. D.; Stern, C. L.; Hupp, J. T. Inorg. Chem. 2005, 44,
8707
32. Benesi, H. A.; Hildebrand, J. H. J. Am. Chem. Soc. 1949, 71, 2703.
33. Murakami, Y.; Kikuchi, J. I.; Suzuki, M.; Matsuura, T. J. Chem. Soc. Perkin Trans.
I, 1988, 1289.