研究生: |
任少緯 Jen, Shao-Wei |
---|---|
論文名稱: |
四價鎳、錳錯合物之合成及鑑定與其質子還原反應之探討 Synthesis, Characterization of Nickel(IV) and Manganese(IV) Complexes and Studies of Their Proton Reduction Performance |
指導教授: |
李位仁
Lee, Way-Zen |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2015 |
畢業學年度: | 103 |
語文別: | 中文 |
論文頁數: | 79 |
中文關鍵詞: | 四價鎳錯合物 、四價錳錯合物 、質子還原反應 |
英文關鍵詞: | Nickel(IV) complexes, Manganese(IV) complexes, Proton reduction |
論文種類: | 學術論文 |
相關次數: | 點閱:137 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 |
此研究延續先前本實驗室許育禎學姊之論文,以兩分子H2PS2三牙配位基製備出Ni(PS2)2 (1),空氣穩定之四價鎳錯合物,並且藉由取代基的修飾以及錳金屬置換,進而合成出一系列鎳及錳四價錯合物,Ni(PS2TMS)2 (2)、Ni(PDMAS2)2 (3)、Mn(PS2)2 (4)、Mn(PS2TMS)2 (5)及Mn(PDMAS2)2 (6)。六個錯合物依據不同電子組態,分別進行NMR及EPR的鑑定,同時,利用紫外光/可見光光譜及X光吸收光譜進行光譜的分析。電化學方面利用循環伏安法鑑定錯合物之氧化還原性質以及探討其應用於質子還原反應性的可能性。
To extend the research of our previously developed six-coordinated Ni(IV) complex supported by two R-PS22- ligand, Ni(PS2)2 (1). The Ni(IV) complex was modified with trimethylsilane and dimethylamino as substituent group. Besides, Mn(IV) complex was also synthesized with the same ligands. Here we present a series of nickel(IV) and manganese(IV) complexes (Ni(PS2TMS)2 (2), Ni(PDMAS2)2 (3), Mn(PS2)2 (4), Mn(PS2TMS)2 (5) and Mn(PDMAS2)2 (6). These complexes was characterized by X-ray crystallography, NMR, EPR, UV-vis spectra, X-ray absorption spectroscopy, and cyclic voltammetry. Cyclic voltammogram revealed two redox waves, which could provide the possibility of two electron reduction to Ni(II) or Mn(II) species. To examine these complexes as potential electrocatalysts for proton reduction, TFA was added to each complex solution and the system was examined by cyclic voltammetry.
1. Vignais, P. M.; Billoud, B.; Meyer, J., FEMS Microbiol. Rev. 2001, 25, 455.
2. Vignais, P. M.; Billoud, B., Chem. Rev. 2007, 107, 4206.
3. Volbeda, A.; Charon, M. H.; Piras, C.; Hatchikian, E. C.; Frey,
M.; Fontecilla-Camps, J. C., Nature 1995, 373, 580.
4. S. Canaguier, V. Artero, M. Fontecave, Dalton Trans. 2008 315.
5. Fre´de´ric Gloaguen, Joshua D. Lawrence, Thomas B. Rauchfuss, J. Am. Chem. Soc. 2001, 123, 9476-9477
6. Matt C. Smith, J. Elaine Barclay, Stephen P. Cramer, Sian C. Davies, Wei-Wei Gu, David L. Hughes, Steven Longhurst David J. Evans, J. Chem. Soc., Dalton Trans., 2002, 2641–2647
7. Vincent Fourmond, Sigolene Canaguier, Benjamin Golly, Martin J. Field, Marc Fontecave, Vincent Artero, Energy Environ. Sci., 2011, 4, 2417–2427
8. Chien-Ming Lee, Chien-Hong Chen, Fu-Xing Liao, Ching-Han Hu, Gene-Hsiang Lee, J. Am. Chem. Soc. 2010, 132, 9256–9258
9. Chien-Ming Lee, Chien-Hong Chen, Shyue-Chu Ke, Gene-Hsiang Lee, Wen-Feng Liaw, J. Am. Chem. Soc.2004, 126, 8406-8412
10. Chien-Ming Lee, Ya-Lan Chuang, Chao-Yi Chiang, Gene-Hsiang Lee, Wen-Feng Liaw, Inorg. Chem. 2006, 45, 10895-10904
11. Tzung-Wen Chiou, Wen-Feng Liaw, Inorg. Chem. 2008, 47, 7908-7913
12. Ya-Ho Chang, Chia-Ling Su, Ru-Rong Wu, Ju-Hsiou Liao, Yi-Hung Liu, Hua-Fen Hsu, J. Am. Chem. Soc. 2011, 133, 5708-5711
13. Paulo Pe´rez-Lourido, Jaime Romero, Jose´A. Garcı´a-Va´zquez, Jesu´s Castro, Antonio Sousa, Lyndsey Cooper, Jonathan R. Dilworth, Raymond L. Richards, Yifan Zheng, Jon A. Zubieta, Inorganica Chimica Acta, 356, 2003, 193-202
14. P. Fernández, J. Romero, J.A. García-Vázquez, A. Sousa-Pedrares, L. Valencia, J. Zubieta, P. Pérez-Lourido Journal of Organometallic Chemistry 2014 750 1-6
15. Paulo Perez-Lourido, Jaime Romero, Laura Rodriguez,
Jose Arturo Garcıa-Vazquez, Jesus Castro, Antonio Sousa,
Jonathan R. Dilworth, Otaciro R. Nascimento, Inorganic Chemistry Communications 2002 5 337–339
16. Hao-Ching Chang, Feng-Chun Lo, Wen-Chi Liu, Tsung-Han Lin, Wen-Feng Liaw, Ting-Shen Kuo, Way-Zen Lee, Inorg. Chem. 2015, 54, 5527−5533
17. M. L. Helm, M. P. Stewart, R. M. Bullock, M. Rakowski DuBois, D. L. DuBois, Science 2011, 333, 863–866.
18. Zhiji Han, William R. McNamara, Min-Sik Eum, Patrick L. Holland, Richard Eisenberg, Angew. Chem. Int. Ed. 2012, 51, 1667 –1670
19. Lu Gan, Thomas L. Groy, Pilarisetty Tarakeshwar, Shobeir K. S. Mazinani, Jason Shearer, Vladimiro Mujica, and Anne K. Jones, J. Am. Chem. Soc. 2015, 137, 1109−1115
20. Souvik Roy, Shobeir K. S. Mazinani, Thomas L. Groy, Lu Gan, Pilarisetty Tarakeshwar, Vladimiro Mujica, Anne K. Jones, Inorg. Chem. 2014, 53, 8919−8929
21. 許育禎 (2006)。含磷硫多牙基之鎳錯合物上之乙腈、硫亞胺酯的轉換與腈水解酶相關之研究。國立臺灣師範大學,台北市。
22. 張智凱 (2010)。含磷硫多牙基之正四價鎳錯合物合成及其光譜探討。國立臺灣師範大學,台北市。
23. Greg A. N. Felton, Richard S. Glass, Dennis L. Lichtenberger, Dennis H. Evans, Inorg. Chem. 2006, 45, 9181−9184
24. Weiwei Gu, Hongxin Wang, Kun Wang, Dalton Trans., 2014, 43, 6406–6413
25. Nicole M. Camasso, Melanie S.Sanford, Science, 2015, 347, 1218
26. Domenick F. Leto and Timothy A. Jackson, Inorg. Chem. 2014, 53, 6179−6194