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| 研究生： |
萬易承 Wan, Yi-Chen |
|---|---|
| 論文名稱： |
以膦及咪唑配位基穩定鎳(III)－硫錯合物 Ni(III)-Thiolate Complexes Stabilized by Phosphine and Carbene Ligand |
| 指導教授： |
廖文峯
Liaw, Wen-Feng |
| 口試委員: |
王雲銘
Wang, Yun-Ming 江明錫 Chiang, Ming-Hsi |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2013 |
| 畢業學年度： | 101 |
| 語文別： | 中文 |
| 論文頁數： | 78 |
| 中文關鍵詞： | 鎳(III)－硫錯合物 |
| 外文關鍵詞： | Ni(III)-Thiolate Complexes |
| 相關次數： | 點閱：3 下載：0 |
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摘要
將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]與tris(1-pyrrolidinyl) phosphine (P(NC4H8)3)反應，合成出中性之[NiIII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (1)。並將其還原生成[PPN] [NiII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (2)。並由UV-Vis光譜儀、X-ray單晶繞射解析，鑑定化合物1及化合物2的結構。
將[PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)]或[NiIII(P(o-C6H3-3-SiMe3-2-S)3)]2與isocyanide (CNCy或CNtBu)反應，合成出中性之[NiIII(CNCy)(P(o-C6H3-3- SiMe3-2-S)3)]與[NiIII(CNtBu)(P(o-C6H3-3-SiMe3-2-S)3)]。並將其還原生成[PPN][NiII(CNCy)(P(o-C6H3-3-SiMe3-2-S)3)] (3)與[K-18-crown-6-ether][NiII(CNtBu) (P(o-C6H3-3-SiMe3-2-S)3)] (4)。並由UV-Vis光譜儀、IR光譜儀、電子順磁共振光譜儀、X-ray單晶繞射解析，鑑定其結構。
選擇低價數的Ni(0)做為活化小分子的金屬來源，以bipyridine為配位基，與CS2反應後，合成出[(bipy)NiII(η2-CS2)] (5)，並以Zn還原(bipy)NiII的方式，再與CS2反應亦可得到化合物5。
The stable nickel(III) complex [NiIII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) was isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and tris(1-pyrrolidinyl) phosphine (P(NC4H8)3). The stable nickel(II) complex [PPN] [NiII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (2) was obtained from reduction of Complex 1. Complex 1 and 2 were characterized by UV-vis and single-crystal X-ray diffraction.
The stable nickel(III) complexes [NiIII(CNCy)(P(o-C6H3-3-SiMe3-2-S)3)] and [NiIII(CNtBu)(P(o-C6H3-3-SiMe3-2-S)3)] were isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] or [NiIII(P(o-C6H3-3-SiMe3-2-S)3)]2 and isocyanide (CNCy or CNtBu). The stable nickel(II) complex [PPN][NiII(CNCy) (P(o-C6H3-3-SiMe3-2-S)3)] (3) and [K-18-crown-6-ether][NiII(CNtBu)(P(o-C6H3-3- SiMe3-2-S)3)] (4) were synthesized by reducing NiIII-CNCy and NiIII-CNtBu. All these complexes were characterized by UV-vis, IR, EPR and single-crystal X-ray diffraction.
Using low valence Ni(0) as small molecule activactor, and bipyridine (bipy) as ligand to react with CS2, [(bipy)NiII(η2-CS2)] (5) can be successfully synthesized. Also, using (bipy)Ni0, reduced from (bipy)NiII species by Zn powder, react with CS2 to produce Complex 5.
Reference
1. Tolman, W. B.; Activation of Small Molecules, Wiley-VCH Press, Weinheim, 2006, pp. XIII-XIV.
2. Debbek, H.; Svetlitchnyi, V.; Gremer, L.; Huber, R.; Meyer, O. Science 2001, 293, 1281.
3. Jeoung, J.-H.; Dobbek, H. Science 2007, 131, 1461.
4. Tommasi, I.; Aresta, M.; Giannoccaro, P.; Quaranta, E.; Fragale, C. Inorg Chim. Acta. 1998, 272, 38.
5. Calabrese, J. C.; Herskovitz, T.; Kinney, J. B. J. Am. Chem. Soc. 1983, 105, 5914.
6. Aresta, M.; Nobile, C. F. J. Chem. Soc. Chem. Commun. 1975, 636.
7. Bristow, G. S.; Hitchcock, P. B.; Lappert, M. F. J. Chem. Soc. Chem. Commun. 1981, 1145.
8. Senn, D. R.; Gladysz, J. A.; Emerson, K.; Larsen, R. D. Inorg. Chem.1987, 26, 2737.
9. Tso, C. T.; Cutler, A. R. J. Am. Chem. Soc. 1986, 108, 6069.
10. Floriani, C.; Fachinetti, G. J. Chem. Soc. Chem. Commun. 1974, 615.
11. Sakaki, S.; Musashi, Y. Inorg. Chem. 1995, 34, 1914.
12. Fachinetti, G.; Floriani, C.; Zanazzi, P. F. J. Am. Chem. Soc. 1978, 100, 7405.
13. Castro-Rodriguez, I.; Nakai, H.; Zakharov, L. N.; Rheingold, A. L.; Meyer, K. Science 2004, 305, 1757.
14. Hoberg, H.; Peres, Y.; Milchereit, A. J. Organomet. Chem. 1986, 307, C38.
15. Angamuthu, R.; Byers, P.; Lutz, M.; Spek, A. L.; Bouwman, E. Science 2010, 327, 313.
16. Pandey, K. K.; Coord. Chem. Rev. 1995, 140, 37.
17. Foye, W. O. J.; Chem. Educ. 1969, 46, 841.
18. Gandhi, T.; Jagirdar, B. R. Inorg. Chem. 2005, 44, 1118.
19. Fehlhammer, W. P.; Mayr, A.; Stolzenberg, H. Angew. Chem. Int. Ed. 1979, 18, 626.
20. Anderson, J. S.; Iluc, V. M.; Hillhouse, G. L. Inorg. Chem. 2010, 49, 10203.
21. Bennett, M. A.; Johnson, J. A.; Willis, A. C. Organometallics. 1996, 15, 68.
22. Haack, P.; Limberg, C.; Tietz, T.; Metzinger, R. Chem. Commun. 2011, 47, 6374.
23. Lam, O. P.; Heinemann, F. W.; Meyer, K. Angew. Chem. Int. Ed. 2011, 26, 5965.
24. Thewissen, D. H. M. W. J. Organometal. Chem. 1988, 188, 211.
25. Qi, J.-S.; Schrier, P. W.; Fanwick, P. E.; Walton, R. A. Inorg. Chem. 1992, 31, 258.
26. Manning, A. R.; Palmer, A. J.; Mcadam, J.; Robinson, B. H.; Simpson, J. Chem. Commun. 1998, 1577.
27. Matsunaga, P. T.; Hillhouse, G. L.; Rherngold, A. L. J. Am. Chem. Soc. 1993, 110, 7215.
28. Wright, A. M.; Wu, G.; Hayton, T. W. J. Am. Chem. Soc. 2012, 134, 9930.
29. Lee, C.-M.; Chuang, Y.-L.; Chiang, C.-Y.; Lee, G.-H.; Liaw, W.-F. Inorg. Chem. 2006, 45, 10895.
30. Lee, C.-M.; Chiou, T.-W.; Chen, H.-H.; Chiang, C.-Y.; Kuo, T.-S.; Liaw, W.-F. Inorg. Chem. 2007, 46, 8913.
31. Teets, T. S.; Nocera, D. G. J. Am. Chem. Soc. 2011, 133, 17796.
32. Lee, C.-M.; Chen, C.-H.; Liao, F.-X.; Hu, C.-H.; Lee, G.-H. J. Am. Chem. Soc. 2010, 132, 9256.
33. Bheemaraju, A. J.; Beattie, W.; Lord, R. L.; Martin, P. D.; Groysman, S. Chem. Commun. 2012, 48, 9595.
34. Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw, J. E.; Goldberg, K. I. Organometallics. 2010, 29, 2176.
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