(44.192.70.216) 您好!臺灣時間:2021/05/09 19:21
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果

詳目顯示:::

我願授權國圖
: 
twitterline
研究生:林雅雯
研究生(外文):yawen Lin
論文名稱:雙核金屬(Cu,Ag)與二硫(硒)磷酸配位基反應性的比較
論文名稱(外文):A Distinct Reactivity Between Dithiophosphates and Diselenophosphates With Dinuclear Metal complexes ( M = Cu,Ag )
指導教授:劉鎮維
指導教授(外文):C.W Liu
學位類別:碩士
校院名稱:中原大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:115
中文關鍵詞:二硒磷酸配位基晶體結構二硫磷酸配位基雙核金屬錯合物
外文關鍵詞:Dinuclear Metal complexescrystall structurediselenophosphatedithiophosphate
相關次數:
  • 被引用被引用:0
  • 點閱點閱:90
  • 評分評分:系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0

中文摘要
本篇論文主要是討論 dtp 配位基和 dsep 配位基與 [M2(□-dppm)2(CH3CN)2][PF6]2 (M = Cu□, Ag□) 反應性的不同。
利用dtp 配位基與 [M2(□-dppm)2(CH3CN)2][PF6]2 (M = Cu□, Ag□) 反應後得到以螯合模式鍵結的 [Cu2(□-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1)、[Ag2(□-dppm)2(S2P(OR)2)2] (R = iPr, 7),架橋模式鍵結的 [Ag4(□-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6) 和懸掛式鍵結的 [Ag3(□-dppm)3(S2P(OR)2)2][PF6] (R = Et, 5)。
當我們將雙核金屬起始物改為利用單核金屬與 dppm 分別加入的方式反應發現,在 Cu 的部分得到相同結果的 [Cu2(□-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1),而在 Ag 的部分則只得到 [Ag4(□-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6)的產物。
有趣的是當我們加入 dsep 配位基,配位基上的 Se 原子會被三配位的P打斷,其化合物為[M(SePPh2CH2PPh2)2][PF6] (M = CuⅠ,3; AgⅠ, 8),這個結果讓我們知道 P-Se 比 P-S 的鍵來的弱。而且他們的 31P NMR 圖譜較特別的是包含了 3J 的耦合,使得圖譜看起來更為複雜。
下列為化合物1, 3, 4, 5, 6, 和8 簡單的晶體資料:
1,orthorhomic, Pbcn, Z = 4, a = 18.5658(11)Å, b = 15.5449(9) Å, c = 24.486(2) Å, V = 7078.3(7) Å3, R1 = 0.0474, wR2 = 0.1311; 3, orthorhomic, P21212, Z = 4, a =20.5638(11) Å, b = 39.594(2) Å, c = 11.9181(6) Å, V = 9694.2(9) Å3, R1 = 0.0472, wR2 = 0.0939; 4, monoclinic, P21/n, Z = 4, a = 14.1504(11)Å, b = 17.8787(13) Å, c = 16.4680(10) Å, V = 4165.9 (5) Å3, R1 = 0.0358, wR2 = 0.0936; 5, orthorhomic, Pna21, Z = 4, a = 32.200(2)Å, b = 18.5101(9) Å, c = 14.5405(7) Å, V = 8666.6 (7) Å3, R1 = 0.0366, wR2 = 0.0930; 6, Orthorhomic, Pbca, Z = 4, a = 17.2672(17)Å, b = 22.7228(17) Å, c = 23.462(2) Å, V = 9205.5 (14) Å3, R1 = 0.0660, wR2 = 0.1478; 8, orthorhomic, Pcca, Z = 4, a = 20.9126(12)Å, b = 11.9598(7) Å, c = 19.6907(12) Å, V = 4924.9 (5) Å3, R1 = 0.0665, wR2 = 0.1306


Abstract
The main theme of this thesis focuses on the reactivity between the reaction of dialkyl dithiophosphate (dtp) and dialkyl diselenophosphate (dsep) with monovalent copper and silver complexes.
While the reaction of NH4S2P(OR)2 and [Cu2(□dppm)2(CH3CN)2] [PF6]2 affords [Cu(□-dppm)2(S2P(OR)2)2] (R = Et, 2; iPr, 1), the analogous reaction of Ag□ produces [Ag4(□-dppm)2(S2P(OR)2)4] (R = Et, 4; iPr, 6), [Ag3(□-dppm)3(S2P(OR)2)2][PF6] (R = Et, 5) and [Ag2(□-dppm)2(S2P(OiPr)2)2], 7. In complexes 1, 2, and 7, a simple chelated bonding mode is observed for the dtp ligands. In cationic, trinuclear silver cage, 5, each edge of the Ag3 plane is bridged by a dppm ligand with the dtp ligands in an unusual bridged-dangling conformation for the two sulfur atoms. As a result, two of the silver atoms in 5 are trigonally coordinated by two P atoms and one S atom. Interestingly, the bonding modes of the dtp ligands for clusters 4 and 6 are also different. Whereas a bridged-chelated pattern for dtp is observed in 4, a bridged-dangling connective pattern is found in two of four dtp in 6. Surprisingly, a one-pot reaction of Ag(CH2CN)4PF6, NH4S2P(OR)2, and dppm produces tetranuclear clusters solely.
When the dialkyl diselenophosphate ligands where incorporated in the reaction, the selsnium atoms abstracted by the tertiary phosphines are uncoverd and compounds of the type, M(SePPh2CH2PPh2)2(PF6), (M = Cu□, 3; Ag□, 8) are isolated. The intriguing 31P-NMR spectra for these mononuclear compounds are also presented.
Pertinent crytallographic date for 1, 3, 4, 5, 6, and 8 are following:
1,orthorhomic, Pbcn, Z = 4, a = 18.5658(11)Å, b = 15.5449(9) Å, c = 24.486(2) Å, V = 7078.3(7) Å3, R1= 0.0474, wR2 = 0.1311; 3, orthorhomic, P21212, Z = 4, a =20.5638(11) Å, b = 39.594(2) Å, c = 11.9181(6) Å, V = 9694.2(9) Å3, R1= 0.0472, wR2 = 0.0939; 4, monoclinic, P21/n, Z = 4, a = 14.1504(11)Å, b = 17.8787(13) Å, c = 16.4680(10) Å, V = 4165.9 (5) Å3, R1= 0.0358, wR2 = 0.0936; 5, orthorhomic, Pna21, Z = 4, a = 32.200(2)Å, b = 18.5101(9) Å, c = 14.5405(7) Å, V = 8666.6 (7) Å3, R1 = 0.0366, wR2 = 0.0930; 6, orthorhomic, Pbca, Z = 4, a = 17.2672(17)Å, b = 22.7228(17) Å, c = 23.462(2) Å, V = 9205.5 (14) Å3, R1 = 0.0660, wR2 = 0.1478; 8, orthorhomic, Pcca, Z = 4, a = 20.9126(12)Å, b = 11.9598(7) Å, c = 19.6907(12) Å, V = 4924.9 (5) Å3, R1= 0.0665, Rw2= 0.1306


目錄
AbstractI
中文摘要III
謝誌V
目錄VI
圖目錄VII
表目錄IX
簡介1
實驗部份6
結果23
合成與反應的探討23
討論31
合成與反應的比較31
晶體結構討論36
31P NMR變溫的探討47
Cu(Sedppm)2(PF6)和Ag(Sedppm)2(PF6)光譜的解析55
結論64
參考資料65
附錄69


參考資料1. (a) Ionel Haiduc; Bryan Sowerby D.; Lu Shao-Fang, Polyhedron 1995 , 14, 3389-3472 (b) Ionel Haiduc; Bryan Sowerby; D., Polyhedron ,1996 ,15 , 2469-25212. (a) Krishman, V.; Zingaro, R. A. J., Coord. Chem. 1971, 1, 1 (b) Krishman, V.; Zingaro, R. A., Inorg. Chem. 1969, 8, 2337 (c) Kudchadker, M. V.; Zingaro, R. A.; Irgolic, K. J., Can. J. Chem.1968, 46, 14153. (a) Kubas, G .J., Inorg. Synth., 1979, 19, 90 (b) Hathaway, B. J.; Holah, D. G.; Postlethwaie, J. D., J. Chem. Soc. 1961, 32154. Liu C.W.; Stubbs, R.; Staples, R. J., Fackler, J. P.; Jr., J. Am. Chem. Soc., 1995, 117, 97785. Liu C. W.; Pitts, J. T.; Fackler, J. P.; Jr, Polyhedron 1997, 16, 3899-39096. Matsumoto Keiji; Tanaka Rika; Nakaom Yasuo; Inorg. Chim. Acta 2000, 304, 293-2967. Liu C. W.; Chen Hsiu-Chih; Wang Ju-Chung; Keng Tai-Chiun, Chem. Commun. ,1998, 18318. Liu C. W.; Hung, C.-M.; Chen, H.-C.; Wang, J.-C.; Keng, T.-C.; Guo, K., Chem. Commun., 2000, 18979. Liu C. W.; Shang, I.-J.; Wang, J.-C.; Keng, T.-C., Chem. Commun., 1999, 99510. Liu C. W.; Liaw, B.-J..; Wang, J.-C.; Keng, T.-C., Inorg. Chem. 2000, 39, 132911. Douglas, M.HO; Bau, R., Inorg. Chem. 1983, 22, 4073-407912. (a) Diez Josefina; Gamasa M. Polar; Gimeno Jose, J. Chem. Soc. Dalton Trans. 1987, 1275 (b) Chaudret B.; Delavaux B.; Poilblanc R., Coordination Chemistry Reviews, 1988, 86, 191-24313. (a) Hathaway, B. J., in Comprehensive Coordination Chemistry,eds. Wilkinson G.; Gillard, R. D.; McCleverty, J.A.; Pergamon, Oxford, 1987, 5 , 533(b) Lancashire, R.J., in Comprehensive Coordination Chemistry,eds. Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Pergamon, Oxford, 1987, 5, 77514. (a) Churchill, M. R.; Kalra, K. L., Inorg. Chem.,1974 , 13 , 1427 (b) Churchill, M. R.; DeBoer, B. G.; Donovan, D. J., Inorg. Chem., 1975, 14, 61715. Churchill, M. R.; Kalra, K. L., Inorg. Chem., 1974, 13, 106516. Theivanayagam, C.; Deivaraj ; Vittal, J. J., J. Chem. Soc., Dalton Trans., 2001, 329-33517. Teo, B. K.; Calabrese ,J. C., Inorg.Chem., 1976 , 15 , 247418. (a) Ahrens, B. and Jones, P. G., Acta Cryst.,1997,C53,1852-1854 (b) Carroll, P. J. and Titus, D. D., J. Chem. Soc., Dalton Trans., 1977, 824 (c) Samuel, O. G.; Edward, D. W., Inorg. Chem., 1980, 19, 1982-198719. Colton, R.; Bernard, F.; Hoskins ; Panagiotidou, P, Aust. J. Chem., 1987, 40, 1909-191220. Bond, A. M.; Colton, R.; Ebner, J. , Inorg. Chem., 1988, 27, 1697-170221. Peringer, P. ; Schwald, J. , J. Chem. Soc., Chem. Commun, 1986, 22, 162522. Jones, P. G. ; Thone, C., Acta Cryst.1992, C48, 2114-211623. (a) Bhattacharyya, P.; Slawin, A. M. Z.; Smith, M. B.; Woollins, J. D., Inorg. Chem., 1996, 35, 3675 (b) Bhattacharyya, P.; Slawin, A. M. Z.; Williams, D. J.; Woollins, J. D., J. Chem. Soc., Dalton Trans., 1995, 318924. (a) Bhattacharyya, P.; Slawin ,A. M. Z.; Williams, D. J.; Woollins, J. D., J. Chem. Soc., Dalton Trans., 1995, 2489 (b) Silvestru, C.; Rosler, R.; Haidac, R.; R. C.-O.; Espinosa, P. R., Inorg.Chem.,1995, 34, 335225. Sreenivase, R. V.; Katti, K. V.; Barnes, C. L., Inorg. Chem., 1995, 34, 548326. Gudat, D.; Daniels, L. M.; Verkade, J. G., Organometallics, 1990, 9, 146427. Matthew, L. C.; Gemma, L. H.; Slawin, A. M. Z.; Woollins, J. D., Inorg. Chem. Commun., 2001, 4, 115-11828. SAINT V4.043: Software for the CCD Dectector System; Bruker Analytical X-ray System: Madisn,WI,1995.29. SAINT V4.035: Software for the CCD Dectector System; Bruker Analytical X-ray System: Madisn,WI,1995.30. AHELXL-97:Sheldrick, G.M. Program for the Refinement of Crystal Structure;University of Göttingen: Göttingen,Germamy,199731. 洪秋明碩士論文, 中原大學,2000.32. Ahrens, B.; Jones, P. G., Z. Naturforsch., Teil B., 1999, 54, 147433. (a) Harvey, P. D.; Drouin, M.; Zhang, T., Inorg. Chem., 1997, 36, 4998(b) Blagg, A., Shaw, B. L.; Thornton-Pett, J. Chem. Soc., Dalton Trans., 1987, 76934. Jitendra, K. B.; Nethaji, M. ; Samuelson, A. G., Inorg. Chem.,1999, 38, 1725-173535. Diez, J.; M. Pilar Gamasa and Gimeno Jose, J. Chem. Soc., Dalton Trans., 1987, 127536. Li, D.; Che C.-M.; Wong, W.-T.; Shieh, S.-J.; Peng, S.-S., J. Chem. Soc., Dalton Trans., 1993, 65337. Harvey, P. D.; Drouin, M.; Zhang, T., Inorg. Chem., 1997, 36, 4998-500538. Yam, V. W. W.; Lam, C.-H.; Cheung, K.-K., Chem. Comm., 2001, 54539. Che, C-M; Mao, Z.; Miskowski, V. M.; Tse, M-C ; Chan, C.-K.; Cheung, K.-K.; Phillips, D. L.; Leung K.-H., Angew. Chem. Int. Ed., 2000, 39, No 22, 408440. Park, J-H ; O'Brien, P ; White, A. J. P. ; Williams, D. J. Inorg. Chem., 2001, 14, 363141. Laila, S. A.; Dilworth, J. R.; Miller, J. R.; Wheatley, N., Inorg. Chim. Acta, 1998, 278, 22942. Dance, I. G.; Scudder, M. L.; Fitzpatrick, L. J., Inorg. Chem., 1985, 24, 254743. Deivarij, T. C.; Lai, G. X.; Vittal, J. J., Inorg. Chem., 2000, 39, 1028-103444. Che, C.-M.; Yip, H.-K.; Li, D.; Peng, S.-M.; Lee, G.-H.; Wang, Y.-M.; Liu S.-T., J. Chem. Soc., Chem. Commun.,1991,161545. Omary, M. A.; Webb, T. R.; Assefa, Z.; Shankle, G. E.; Patterson, H. H., Inorg. Chem., 1998, 37, 1380-138646. Theivanayagam, C. Deivaraj ; Vittal, J. J., J. Chem. Soc., Dalton Trans., 2001, 322-32847. Franzoni, D.; Pelizzi, G.; Predieri, G.; Tarasconi, P., Vitali, F., Pelizzi, C. J.; J. Chem. Soc., Dalton Trans., 1989, 24748. (a) Schubert, U.; Neugebauer, D.; Aly, A. A. M. Z., Anorg. Allg. Chem., 1980, 464, 217 (b) Aly, A. A. M.; D. Neugebauer; Orama O.; Schubert, H., Angew. Chem. Int. Ed. 1978, 17, 12549. Wang, C.-F.; Peng, S.-M.; Chan,C.-K.; Che C.-M., Polyhedron, 1996, 15, 185350. Leung, W.-H.; Lau, K.-K.; Zhang, Q.-F.; Wong, W.-T.; Tang, B., Organometallics , 2000, 19(11), 2084-2089

QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top
1. 12.藍瀛芳,仲裁協議的法定要件及其效果,仲裁季刊,第57期,6.1.2000。
2. 13.藍瀛芳,合約內仲裁條款與管轄條款併列的問題─我國法院與英格蘭法院以及香港法院在實務上的差異,仲裁季刊,第54期,9.10,1999。
3. 11.藍瀛芳,混合式的仲裁程序,商務仲裁季刊,第50期。
4. 3.黃正宗,仲裁程序之研究,仲裁季刊,第54期,9.10,1999。
5. 李啟明〈1998〉‧心臟衰竭治療的診斷與治療‧當代醫學,25〈5〉,352-355。
6. 李克威、楊茂勳、丁予安〈1993〉‧心臟衰竭的臨床表徵‧國防醫學,17〈3〉,195-199。
7. 10.藍瀛芳,簡述"訴訟外解決爭議的方法"(A.D.R.),商務仲裁季刊,第44期。
8. 9.劉錦華,貿易糾紛與商務仲裁,商務仲裁季刊,第49期。
9. 8.劉錦華,仲裁法立法經過與要旨,全國律師,八十七年10月。
10. 7.嵇珮晶、吳光明,論仲裁與調解之結合,仲裁季刊,9.1.2000, 第58期。
11. 5.黃茂榮,電子商務契約的一些法律問題,萬國法律,No.110 2000.4。
12. 4.黃正宗,我國仲裁協會及企業依聯合國國際貿易法委員會仲裁規則(UNCITRAL Arbitration Rules 1976)進行仲裁之可行性研究,仲裁季刊,第59期,11.30.2000。
13. 2.范光群,大陸仲裁法的評介及其與台灣商務仲裁制度的比較,商務仲裁季刊,第三十八期。
14. 賴文源(1993)‧心臟衰竭功能的評估‧國防醫學,17(3),201-207。
15. 柯乃熒、蕭琪、許淑蓮〈1997〉‧不確定感之概念分析‧護理雜誌,
 
系統版面圖檔 系統版面圖檔