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| 研究生： |
蔡宜興 Y.-S. Tsai |
|---|---|
| 論文名稱： |
多磷配子的合成與十二羰基四銠衍生物的合成及結構研究 Sytheses of Multidentate Phosphine Ligands ;Syntheses and Crystal Structure of Tetrarhodium Dodeccarbonyl Derivatives |
| 指導教授： |
翁春和
Ueng, Chuen-Her |
| 學位類別： |
碩士 Master |
| 系所名稱： |
化學系 Department of Chemistry |
| 畢業學年度： | 87 |
| 語文別： | 中文 |
| 論文頁數： | 80 |
| 中文關鍵詞： | 多磷配子 |
| 英文關鍵詞： | Multidentate Phosphine Ligands |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：290 下載：1 |
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十二羰四銠[Rh4(CO)12]與含磷雙牙配子Ph2P(CH2)nPPh2(n = 2，dppe；n = 4，dppb)，經由熱裂法反應共得到三個錯合物：[Rh4(CO)8(Ph2PCH2CH2CH2CH2PPh2)2 (1)、[Rh4(CO)10(Ph2PCH2CH2PPh2)] (2)、[Rh4-(CO)8(Ph2PCH2CH2CH2CH2PPh2)2] (3)；其中(1)、(2)已由X射線單晶繞射獲得晶體結構，錯合物(3)則由紅外線光譜推測其結構。
化合物(1)，三個橋鍵羰基維持不變，磷原子取代了兩個銠原子的終端羰基；化合物(2)、(3)，每一個銠原子的終端羰基均被磷原子取代。晶體數據:(1)為單斜晶系，空間群 P21/a，a = 23.061(3)A，b =11.956(2) A，c =24.945(2) A，β= 95.742(9)°，最後 Rf = 0.04 (7947個繞射點)；(2)為單斜晶系，空間群P21/n，a = 12.651(2) A，b =18.879(2) A，c =18.748(3) A，β=98.752(3)°最後Rf = 0.033 (5258個繞射點)。
根據R.B.King合成多磷配子的方法，合成新的五磷配子
(Ph)(Ph2PCH2CH2)P(CH2)2P(CH2CH2PPh2)2以及六磷配子 (Ph2PCH2CH2)2P(CH2)5P(CH2CH2PPh2)2。
Reactions of [Rh4(CO)12] with Ph2P(CH2)nPPh2 (n = 2 , dppe ; n = 4 , dppb) by the thermolytic method yield three complexes :
[Rh4(CO)10(Ph2PCH2CH2CH2CH2PPh2)] (1), [Rh4(CO)8(Ph2PCH2CH2PPh2)2 (2), [Rh4(CO)8 (Ph2PCH2CH2CH2CH2PPh2)2] (3) . Crystal structures of complexes (1) and (2) have been determined by X-ray diffraction method .
For compound (1) , the set of three bridging CO groups along one triangular set of edges are retained , but two terminal CO groups on two rhodium atoms are replaced by two phosphorus atoms . For compound (2) and (3) , one terminal carbonyl group on each rhodium atom is replaced by a phosphorus atom . Crystal data : (1), monoclinic space group P21/a , a = 23.061(3) A， b = 11.956(2) A，c = 24.945(2) A，β= 95.742(9)°. Final Rf = 0.049 for 7947 reflections . (2), monoclinic space group P21/n , a = 12.651(2) A， b = 18.879(2) A， c = 18.748(3) A， β= 98.752(3)°. Final Rf = 0.033 for 5258 reflections .
The compounds , (Ph)(Ph2PCH2CH2)P(CH2)2P(CH2CH2PPh2)2 and (Ph2PCH2CH2)2P(CH2)5P(CH2CH2PPh2)2] were synthesized according to the published method .
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