臺灣博碩士論文加值系統

本研究製備出含雙鈷之氮、磷雙牙配位基[(μ-PPh2CH2PPh2)Co2 (CO)4(μ,η-Me2NCH2C≡CPCy2)] 4c 。化合物 4c 比單純全磷配位基較不容易氧化。利用氮和金屬鍵結較弱，且磷和鈀金屬配位能力較強，使此雙牙基配位能力一強一弱的特性，進而影響催化反應效率的效率。 吾人嘗試將化合物4c 當鈀金屬之配位基形成之催化劑，應用在胺化反應和Suzuki耦合反應上，結果顯示此含氮、磷異核雙牙基比同核雙牙基在催化反應上有更好的效果。

A cobalt-containing bidentate ligand [(μ-P, P-PPh2CH2PPh2)Co2(CO)4 (μ,η-Me2NCH2C≡CPCy2 ] 4c bearing phosphino- and amino-sites in catalytic reactions was prepared. The advantages of employing phosphines having P,N coordinating sites are obvious. For one thing, this P,N bidentate ligand is less air-sensitive than purely phosphines. What is more, the relatively easy formation/breaking of the nitrogen-metal bond of P,N coordinated metal centre is an useful feature in various catalytic reactions. Their capacities as more effective chelating ligands than diphosphines in the palladium complexes catalyzed amination and Suzuki cross coupling reaction were observed.

目錄-------------------------------------------------- iii
表目錄------------------------------------------------ vi
圖目錄------------------------------------------------ viii
一、 序論----------------------------------------- 1
(一) 　耦合反應-------------------------- 1
(二) 　Suzuki 耦合反應------------------- 3
(三) 　胺化反應-------------------------- 6
(四) 　過渡金屬配位基-------------------- 9
(五) 　研究動機-------------------------- 14
二、 結果與討論--------------------------------- 17
(一) 　含鈷金屬氮磷雙牙配位基合成與研究
[(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2C≡CP(Cy)2)]4c-----17

(二) 　含鈀、鈷金屬氮磷錯合物的合成與研究
[(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2C≡CP(tBu)2)PdCl2] 5c 、
[(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2C≡CP(tBu)2)Pd(η1-C5H5)2] 5ccp 、
[(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2C≡CP(Cy)2)Pd(η3-C3H5)]+[(η3-C3H5)PdCl2]- 7c 及
[(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2C≡CP(Cy)2)Pd(η3-C3H5)]+[BF4]- 7cB -------------------------------------------20
(三) 　含鈷金屬氮磷雙牙配位基4c應用在胺化反應--------------------------------------------------------25
(四) 　含鈀、鈷金屬氮磷雙牙配位基7c應用在胺化反應---------------------------------------------------32
(五) 　含鈷金屬氮磷雙牙配位基4c應用在Suzuki 耦合反應-----------------------------------------------33
(六) 化合物7c 的電荷分佈研究------------39

三、 結論--------------------------------------------42
四、 實驗------------------------------------------- 44
(一)儀器與藥品--------------------------------45
(二)操作技巧方法與性質------------------------49
(三)合成與鑑定--------------------------------50
(四)　針對aryl bromides 及 morpholine 進行Amination 反應的步驟-----------------------------------61
(五)　針對 aryl bromide 進行Suzuki 耦合反應的步驟--------------------------------------------------------63
(六)　密度泛函數(Density Functional Theory)計算----------------------------------------------------------64
參考文獻-----------------------------------------------65
附錄---------------------------------------------------69
光譜數據-------------------------------------------70
晶體數據-------------------------------------------94
產物光譜數據---------------------------------------121

1.(a) Colacot, T. J., Chem. Rev. 2003, 103, 3101. (b) Jutand, A. Eur. J. Inorg. Chem. 2003, 2017. (c) Christmann, U.; Vilar, R. Angew. Chem. Int. Ed. 2005, 44, 366.
2.(a) Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 1998, 37, 3387. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722.
3.(a) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (b) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem. Int. Ed. 2005, 44, 2. (c) Cardenas, D. J. Angew. Chem. Int. Ed. 2003, 42, 384.
4.(a) Frisch, A. C.; Beller, M. Angew. Chem. Int. Ed. 2005, 44, 674. (b) Tolman, C. A. Chem. Rev. 1997, 77, 313. (c) Van Leeuwen, P. W.; Kamer, P. C. J.; Reek, J. N. H.; Dierkes, P. Chem. Rev. 2000, 100, 2741.
5.(a) Iqbal, J.; Bhatia, B.; Nayyar, N. K. Chem. Rev. 1994, 94,519. (b) Grushin, V. V.; Alper, H. Chem. Rev. 1994, 94, 1047.
6.(a) Negwer, M., Organic-chemical drugs and their synonyms, 7th ed.; (b) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D., Angew. Chem. Int. Ed. 2005, 44, 4442-4489. (c) Loutfy, R. O.; C. Hsiao, K.; Kazmaier P. M., Photogr. Sci. Eng., 1983, 27, 5-9. (d) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L., J. Am. Chem. Soc. 2005, 127, 4685-4696. (e) D’Aprano, G.; Leclerc, M.; Zotti, G.; Schiavon, G., Chem. Mater. 1995, 7, 33-42.
7.(a) Kramareva, N.; Navarro, O.; Nolan. S. P., Org. Lett. 2005, 9, 1829. (b) Yin, J.; Rainka, M. P.; Zhang, X. X.; Buchwald, S. L., J. Am. Chem. Soc. 2002, 124, 1162. (c) Zhou, J.; Fu, G. C., J. Am. Chem. Soc. 2004, 126, 1340.
8.(a) Zhang, F. Y.; Pai, C. C.; Chan, A. S. C. J. Am. Chem. Soc. 1998, 120, 5808. (b) Lira, R.; Wolfe, J. P. J. Am. Chem. Soc. 2004, 126, 13906. (c) Miura , M. Angew. Chem. Int. Ed. 2004, 43, 2201.
9.(a) Atkinson, R. C.; Gibson, V. C.; Long, N. J. Chem. Rev. 2004, 33, 313. (b) Marcoux, J. F.; Wagaw, S.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1568.
10. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
11. Bedford, R. B.; Cazin, C. S., Chem. Comm. 2001, 11, 1540.
12. Kosugi, M.; Kameyama, M.; Sano, H.; Migita, T., Chem. Lett. 1983, 927.
13. Hartwig, J. F., Angew. Chem. Int. Ed. 1998, 37, 2046.
14. Verkade, J. G., J. Org.Chem. 2003, 68, 8416.
15. Hung, W. Y.; Liao, Y. L.; Hou, T. H.; Lin, C. Y.; Wong, K. T., Chem. Mater. 2007, 19, 6350.
16. (a) Crudden, C. M.; Allen, D. P., Coordination Chemistry Reviews 2004, 2247. (b) Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 42, 1290. (c) Gonz´alez, S. D.; Nolan, S. P., Coordination Chemistry Reviews 2007, 251, 874.
17. Berthod, M.; Mignani, G.; Woodward, G.; Lemaire, M., Chem. Rev. 2005, 105, 1801.
18. Helmut, W., Organometallics 2005, 24, 1036.
19. (a) Chang, Y. C.; Chang, C. P.; Huang, Y. L.; Hong, F. E., Dalton Trans 2004, 157. (b) Chang, C. P.; Huang, Y. L.; Hong, F. E., Tetrahedron 2005, 61, 3835. (c) Chang, Y. C.; Lee, J. C.; Hong, F. E., organometallic 2005, 24, 5686. (d) Lee, J. C.; Wang, M. G.; Hong, F. E., Eur. J. Inorg. Chem. 2005, 5011.
20. Braunstein , P., J. Organomet. Chem. 2004, 689, 3953.
21. Parr, R. G.; Pearson, R. G., J. Am. Chem. Soc. 1983, 105, 7512.
22. Gajare, A. S.; Toyota, K.; Yoshifuji, M.; Ozawa, F., Chem. Commun. 2004, 1994.
23. 李堅呈, 碩士論文, 中興大學化學研究所,2005
24. Braunstein, P., J. Organomet. Chem. 2004, 689, 3953–3967
25. 蕭有成, 碩士論文, 中興大學化學研究所, 2007
26. Crystal structures for related compounds are available from literature: (a) R. Fernández-Galán, F. A. Jalón, B. R. Manzano, J. Rodríguez-de la Fuente, M. Vrahami, B. Jedlicka, W. Weissensteiner, G. Jogl, Organometallics, 1997, 16, 3758. (b) I. C. F. Vasconcelos, N. P. Rath, C. D. Spilling, Tetrahedron: Asymmetry, 1998, 9, 937. (c) Y. Wang, X. Li, J. Sun, K. Ding, Organometallics, 2003, 22, 1856. (d) J. W. Faller, N. Sarantopoulos, Organometallics, 2004, 23, 2008. (e) B. Goldfuss, T. Löschmann, F. Rominger, Chem. Eur. J., 2004, 10, 5422.
27. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 4th ed., Chap. 5, John Wiley & Sons, New York, 2005.
28. Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.