簡易檢索 / 詳目顯示
| 研究生： |
蘇廷錡 Su, Ting-Chi |
|---|---|
| 論文名稱： |
雙金屬合作效應：單取代炔類化合物經立體與區域選擇性的碳-碳耦合反應以形成二聚物的研究 Dimetallic Cooperativity in Regio and Steroselective C－C coupling to form Dimers of Monosubstituted Acetylenes |
| 指導教授： |
許拱北
Shiu, Kom-Bei |
| 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： | 2014 |
| 畢業學年度： | 102 |
| 語文別： | 中文 |
| 論文頁數： | 129 |
| 中文關鍵詞： | PhC≡CH 、TolC≡CH 、碳-碳耦合 、Regio- and Stero-select |
| 外文關鍵詞： | Terminal alkynes, C－C coupling complexes, Regio-and Stero-selection |
| 相關次數： | 點閱：135 下載：7 |
| 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 |
以[Ru2(μ-dppm)2(μ-OAc)(CO)4][PF6] (1)與PhC≡CH和TolC≡CH炔類在室溫下反應，分別得到錯合物[Ru2(μ-dppm)2(μ-η1,η2-C2R) (CO)4][PF6] ( R = Ph (2)；Tol (3) )；將錯合物2和3與TMNO•2H2O反應，得到 [Ru2(μ-dppm)2(μ-η1,η2-C2R)(CO)3(MeCN)][PF6] ( R = Ph (5)；Tol (6) )。錯合物1分別與PhC≡CH和TolC≡CH在MeOH下迴流，得到碳－碳原子間耦合[Ru2(μ-dppm)2(μ-η1,η2-C2Ph)(CO)2 (μ-η2,η2-PhCH＝C－C≡CPh)] (7)、[Ru2(μ-dppm)2(CO)3(μ-η2,η2-PhC＝CH－C≡CPh)][PF6] (8) 和[Ru2(μ-dppm)2(μ-η1,η2-C2Tol) (CO)2(μ-η2,η2-TolHCCCCTol)] (9)，錯合物1與PhCH2C≡CH迴流，得到是[Ru2(μ-dppm)2(CO)4(μ-η1,η2- C2CH2Ph)] [PF6] (4)，不是碳-碳耦合結構。錯合物2分別與TolC≡CH和PhCH2C≡CH迴流，得到 [Ru2(μ-dppm)2(CO)3(μ-η2,η2-PhCCCHCTol)] [PF6] (10)、[Ru2(μ-dppm)2(CO)3(μ-η2,η2-PhCCCHCCH2Ph)] [PF6] (11)和[Ru2(μ-dppm)2(CO)2(μ-CO)( μ-CCHCHPh)(μ-η2,η2-Ph CCCCHCH2Ph)] (12)。透過反應產物不同，可以觀察出這一類反應有Regio- and Stero-select現象產生。
The reaction of [Ru2(μ-dppm)2(μ-OAc)(CO)4][PF6] (1) with terminal alkynes RC≡CH in room temperature gives the alkyne complexes [Ru2(μ-dppm)2(μ-η1,η2-C2R)(CO)4][PF6] ( R = Ph (2)；Tol (3) ) . complex 1 reacts with terminal alkynes RC≡CH ( R = Ph；Tol ) in MeOH reflux to give C－C coupling complexes [Ru2(μ-dppm)2(μ-η1,η2-C2Ph)(CO)2 (μ-η2,η2-PhCH＝C－C≡CPh)] (7), [Ru2(μ-dppm)2(CO)3(μ-η2,η2-PhC＝CH－C≡CPh)][PF6] (8) and [Ru2(μ-dppm)2(μ-η1,η2-C2Tol)(CO)2(μ-η2,η2-TolHCCCCTol)] (9), but complex 1reacts with PhCH2C≡CH in MeOH reflux to give [Ru2(μ-dppm)2(CO)4(μ-η1,η2- C2CH2Ph)][PF6] (4), not C－C coupling complexes. Use complexes 2, 3 and 4 with terminal alkynes RC≡CH, which R are not identical with their ligand in MeOH reflux to give another C－C coupling complexes. Through different reaction product, can disscuss reaction pathways and explore this type of reaction is observed with the regio-and stero-selection.
[1]. J-Y.Salaun, P.Laurent, H.des.Abbayes, Coord.Chem.Rev.1998, 353, 178-80.
[2]. http://en.wikipedia.org/wiki/Coupling_reaction
[3]. Carl Glaser, Annalen der Chemie und Pharmacie, 1870, 154, 137.
[4]. Chodkiewicz, W., Ann. Chim. Paris 1957, 2, 819–69.
[5]. R. D. Stephens, C. E. Castr, J. Org. Chem., 1963, 28, 3313-5.
[6]. M. Eckhardt, G. C. Fu, J. Am. Chem. Soc., 2003, 125, 13642–3.
[7]. Beata Powała • Cezary Pietraszuk, Catal Lett 2014,144,413-8
[8]. Tsugio Kitamura, Tetrahedron Letters 2005, 46,3823–7
[9]. David R. Spring, Chem. Eur. J. 2012, 18, 8774 –9.
[10]. George G. Stanley, Science. 1993,260,1784-8.
[11]. Puddephatt, Orga nometallic.Chem.2000, 77, 593-594.
[12]. Raymond J. Haines, Journal of Organometallrc Chemistry, 1984,275, 99- 111.
[13]. F.A.Cotton, G.Wilkinson, C.A.Murillo, M.Bochmann, Advanced Inorganic Chemistry 6th ed., Wiley,New York,1999.
[14]. Puddephatt, Organometallics 1994,13, 3063-7
[15]. Puddephatt, Dalton Trans. 2003, 261–265.
[16]. Raymond J. Haines, J.Chem.Soc. , Dalton Trans. 1993, 3749-57.
[17]. Martin Cowle, Organometallics 1988, 7, 1663-6.
[18]. Shiu, Kom-Bei, Organometallics, 1997, 16,114 – 9.
[19]. F.A Cotton, Inorg. Chem. 1981, 20, 3543-55.
[20]. Selby A. R. Knox, J. Chem. Soc., Dalton Trans. 1983, 2661-8.
校內：2019-08-18公開校外：2019-08-18公開