臺灣博碩士論文加值系統

RuCl2(POMe)2 (POMe = diphenyl(2-methoxyphenyl)phosphine) 的製備與特性都已經被完整的報導過了。然而，把RuCl2(POMe)2在RCN (R = Me, Et) 溶劑下加熱迴流，就會導致兩個CH3Cl的離去生成化合物Ru(RCN)2(PO)2 (R = Me(1), Et(3))，則從未有人研究過。如果在反應裡加入KPF6 或者 KBF4 就會得到額外的產物[Ru(RCN)2(PO)(POMe)]+ (R = Me(2), Et(4))；依反應溶劑的選擇而定。化合物2和4的去烷化反應同時包含CH3Cl和[CH3(POMe)]+ 的路徑。經由NMR和ESI-mass光譜的追蹤可以幫助我們清楚了解釕錯合物的去烷化路徑。化合物1、2和3都成功地解出X-ray結構。

The preparation and characterization of RuCl2(POMe)2 (POMe = diphenyl(2-methoxyphenyl)phosphine) was reported. However, the reactions of RuCl2(POMe)2 with refluxing RCN (R = Me, Et) led to loss of CH3Cl to give Ru(RCN)2(PO)2 (R = Me(1), Et(3)), which are never reported. Adding KPF6 or KBF4 in the reactions will give additional products [Ru(RCN)2(PO)(POMe)]+ (R = Me(2), Et(4)) according to the solvent selection. Complexes 2 and 4 were observed the dealkylating via loss of CH3Cl or [CH3(POMe)]+ pathways. The [CH3(POMe)]+ pathway needs excess POMe which may come from the thermal decomposition of [RuCl(POMe)2(RCN)]+. The NMR and ESI-mass monitoring spectra also help us to understand the Ru complexes dealkylation pathway. The structures of 1, 2, and 3 were confirmed by X-ray analyses.

目錄
第壹章 緒論 1
1.1 簡介 1
1.2 研究動機與研究問題 6

第貳章 結果與討論 10
2.1 Ru(MeCN)2(PO)2 (1) 的合成 11
2.2 [Ru(MeCN)(PO)(POMe)]PF6 (2) 的合成 16
2.3 Ru(EtCN)2(PO)2 (3) 的合成 19
2.4 [Ru(EtCN)(PO)(POMe)]BF4 (4) 的合成 22
2.5 [Ru(CN)3(POMe)2]PPh4 (5) 的合成 22

第参章 活化路徑的探討 27
3.1 NMR 追蹤實驗 27
3.2 ESI-Mass 追蹤實驗 34
3.3 結論 35

第肆章 實驗部分 38
4.1 試藥來源及前處理 38
4.2儀器部分 40
4.3 實驗步驟 41
4.3-1 Ru(RCN)2(PO)2 (R=Me (1), Et (3)) 41
4.3-2 [Ru(RCN)2(PO)(POMe)]PF6 的合成(R=Me (2), Et (4)) 42
4.3-3 [Ru(CN)3(POMe)2]PPh4 (5)的合成 43
4.3-4 Re(CO)3L2Br 的合成 43
4.3-5 [Re(CO)3L3]BF4 的合成 44
參考文獻 46

(1)Boom, M. E. v. d.; Liou, S.-Y.; Ben-David, Y.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 1998, 120, 6531-6541.
(2)Maercker, A. Angew. Chem., Int. Ed. Engl. 1987, 26, 972-989.
(3)Milstein, D. Acc. Chem. Res. 1984, 17, 221-226.
(4)Khumtaveeporn, K.; Alper, H. Acc. Chem. Res. 1995, 28, 414-422.
(5)Aye, K.-T.; Colpitts, D.; Ferguson, G.; Puddephatt, R. J. Organometallics 1988, 7, 1454-1456.
(6)Zlota, A. A.; Frolow, F.; Milstein, D. J. Am. Chem. Soc. 1990, 112, 6411-6413.
(7)Rondon, D.; Chaudret, B.; He, X. D.; Labroue, D. J. Am. Chem. Soc. 1991, 113, 5671-5676.
(8)Tolman, C. A.; Ittel, S. D.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1979, 101, 1742-1751.
(9)Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577-7586.
(10)Yamamoto, Y.; Sato, R.; Ohshima, M.; Matsuo, F.; Sudoh, C. J. Organomet. Chem. 1995, 489, C68-C70.
(11)Yamamoto, Y.; Sato, R.; Matsuo, F.; Sudoh, C.; Igoshi, T. Inorg. Chem. 1996, 35, 2329-2336.
(12)Han, X.-H.; Yamamoto, Y. J. Organomet. Chem. 1998, 561, 157-165.
(13)Ueno, S.; Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516-16517.
(14)Rogers, C. W.; Patrick, B. O.; Rettig, S. J.; Wolf, M. O. J. Chem. Soc., Dalton Trans. 2001, 1278-1283.
(15)Komiya, S.; Hirano, M. Dalton Trans. 2003, 1439-1453.
(16)Hirano, M.; Sato, H.; Kurata, N.; Komine, N.; Komiya, S. Organometallics 2007, 26, 2005-2016.
(17)Blair, S.; Izod, K.; Clegg, W.; Harrington, R. W. Inorg. Chem. 2004, 43, 8526-8531.
(18)Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658-2666.
(19)Rogers, C. W.; Wolf, M. O. Chem. Commun. 1999, 2297-2298.
(20)Halpern, J.; Harrod, J. F.; James, B. R. J. Am. Chem. Soc. 1961, 83, 753-754.
(21)Jones, C. E.; Shaw, B. L.; Turtle, B. L. J. Chem. Soc., Dalton Trans. 1974, 992-999.
(22)Yamamoto, Y.; Suzuki, H.; Tajima, N.; Tatsumi, K. Chem. Eur. J. 2002, 8, 372-379.