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| 研究生： |
賴政國 |
|---|---|
| 論文名稱： |
六磷配子與含磷錯合物之合成及結構研究 Syntheses and Crystal Structures of Metal Complexes Containing Hexadentate Phosphine Ligands |
| 指導教授： | 翁春和 |
| 學位類別： |
博士 Doctor |
| 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： | 323 |
| 中文關鍵詞： | 六磷配子 、含磷錯合物 |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：167 下載：1 |
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雙鐵錯合物[[Fe2(CO)4(η5-C5H5)2]與含磷雙牙配子Ph2P-(CH2)nPPh2 (n=1,dppm; n=2, dppe; and n=3, dppp)，經由熱裂法反應，共得到四個二取代的錯合物：[{Fe(CO)(η5-C5H5)}2dppm](1), [{Fe(CO)(η5-C5H5)}2dppe](2),[{Fe(CO)(η5-C5H5)}2dppp](3)及[{Fe(η5-C5H5)C1}dppp](4)。
十二羥四銥[Ir4(CO)12]與含磷雙牙配子{Fe(C5H4PPh2)2}(dppf)經由熱裂法反應共得到五個錯合物：[HIr4(CO)7{Fe(C5H4PPh2)2}{Fe(C5H4PPh2)-(C5H3PPh2)}](5), [H2Ir4(CO)6-{Fe(C5H4PPh2)(C5H3PPh2)}2](6), [H3Ir4(CO)4{Fe(C5H4PPh2)(C5H3PPh2)}-{Fe(C5H4)(C5H4P(Ph)(C6H4)}{P(Ph)(C6H4)}](7), [H4Ir4(CO)4{Fe(C5H3PPh2)-(C5H4P(Ph)(C6H4)}2](8)及[Ir4(CO)8(dppf)2](9)。
六羥金屬 M(CO)6(M: Cr, Mo, W)及鎳鹽 NiX2(X: C1, Br, I)與六磷配子[(Ph2PC2CH2)2P(CH2)2P(CH2CH2PPh2)2(P2(-Pf)4)及[(Ph2PCH2CH2)2P(CH2)3P(CH2CH2PPH2)2](P2(-Pf)4')經由化學氧化法及熱裂法共得到九個錯合物：[{W(CO)5}6P2(-Pf)4](10), [{Cr(CO)3}2P2(-Pf)4](ll), [{Mo(CO)3}2-P2(-Pf)4'](12), [(NiC1)2P2(-Pf)4][PF6]2(13), [(NiC1)2P2(-Pf)4'][PF6]2(14),[(NiBr2)2P2(-Pf)4](15), [(NiBr)(NiBr2)P2(-Pf)4][PF6](16), [(NiBr)2-P2(-Pf)4[PF6]2(17) and [(NiI2)2P2(-Pf)4'](18)。錯合物(l)~(8)，(10)~(18)以X射線單晶繞射的方法獲得單晶結構解析。晶體數據整理如表 0.1。
Treatments of [Fe2(CO)4(η5-C5H5)2] with diphosphine ligands, Ph2P-(CH2)nPPh2 (n=1, dppm; n=2, dppe; and n=3, dppp), via thermoiyticmethod afford four disubstituted compounds: [{Fe(CO)(η5-C5H5)}2dppm](1), [{Fe(CO)(η5-C5H5)}2dppe](2), [{Fe(CO)(η5-C5H5)}2dppp](3) and[{Fe(η5-C5H5)C1}dppp](4). The reactions of [Ir4(CO)12] with{Fe(C5H4PPh2)2}(dppf) by thermolytic method yield five compounds:[HIr4(CO)7{Fe(C5H4PPh2)2}{Fe(C5H4PPh2)(C5H3PPh2)}](5), [H2Ir4(CO)6-{Fe(C5H4PPh2)(C5H3PPh2)}2](6), [H3Ir4(CO)4{Fe(C5H4PPh2)(C5H3PPh2)}-{Fe(C5H4)(C5H4P(Ph)(C6H4)}{P(Ph)(C6H4)}](7), [H4Ir4(CO)4{Fe(C5H3PPh2)-(C5H4P(Ph)(C6H4)}2](8) and [Ir4(CO)8(dppf)2](9).
By chemical oxidation and thermoiytic methods, the reactions of M(CO)6(M: Cr, Mo, W) and NiX2(X: C1, Br, I) with hexadentate phosphine ligands [(Ph2PC2CH2)2P(CH2)2P(CH2CH2PPh2)2(P2(-Pf)4) and [(Ph2PCH2CH2)2P(CH2)3P(CH2CH2PPH2)2](P2(-Pf)4'), yield nine compounds: [{W(CO)5}6P2(-Pf)4](10), [{Cr(CO)3}2P2(-Pf)4](ll), [{Mo(CO)3}2- P2(-Pf)4'](12), [(NiC1)2P2(-Pf)4][PF6]2(13), [(NiC1)2P2(-Pf)4'][PF6]2(14), [(NiBr2)2P2(-Pf)4](15), [(NiBr)(NiBr2)P2(-Pf)4][PF6](16), [(NiBr)2-P2(-Pf)4[PF6]2(17) and [(NiI2)2P2(-Pf)4'](18).
All compounds except (9) have been characterized by X-ray diffraction method and their crystal data are listed on Table 0.1.
