研究生: |
陳鴻文 Hong-Wen Chen |
---|---|
論文名稱: |
含第16族元素(S、Se、Te)之過渡金屬(Mn、Fe、Ru)團簇化合物的合成與其化性、物性的研究 |
指導教授: |
謝明惠
Shieh, Ming-Huey |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 261 |
中文關鍵詞: | 金屬團簇化合物 |
英文關鍵詞: | Transition Metal |
論文種類: | 學術論文 |
相關次數: | 點閱:153 下載:9 |
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[Et4N]2[SeFe3(CO)9]與Cu+ 試劑的反應,不同的Cu+ 來源,可生成不同的產物:與[Cu(CH3CN)4]BF4的反應可生成{[SeFe3(CO)9]2
-Cu}3-,與CuOAc反應可生成{[SeFe3(CO)9]2Cu2(μ-OAc)}3-。另外混合dppm與dppe於[SeFe3(CO)9]2-與[Cu(CH3CN)4]BF4的反應中,利用反應溶劑以及反應物比例的不同,可生成一系列含Cu片段的化合物(μ5-Se)Fe3(CO)9Cu2(μ-dppm)(L) (L = CH3CN, THF)、SeFe3(CO)9Cu2
-(μ-dppe)、{[SeFe3(CO)9]2Cu2(μ-dppe)}2-和{[SeFe3(CO)8]Cu2(μ-dppm)
-(μ-dppm)}。
以Se powder和Mn2(CO)10於鹼性溶液中在室溫下反應,不同的濃度及反應時間,可得到不同的結果:於0.9 M KOH下以Se: Mn = 1: 1比例反應一小時,可得到[Se10Mn6(CO)18]4-;若將KOH濃度提高至4 M,則可得到[Se2Mn3(CO)9]2-。以Se: Mn = 10: 6比例,於0.9 M KOH和4 M KOH濃度下反應一小時,皆可得到[Se10Mn6(CO)18]4-;若延長反應時間至十天,於0.9 M KOH下可得[Se5Mn4(CO)12]2-,而於4 M KOH下可得到[Se6Mn6(CO)18]4-,二者皆為新型結構之化合物。
The reactions of [Et4N]2[SeFe3(CO)9] with different Cu+ reagents resulted in different products. When [Et4N]2[SeFe3(CO)9] reacted with
[Cu(CH3CN)4]BF4 and CuOAc, {[SeFe3(CO)9]2Cu}3- and {[SeFe3 -(CO)9]2Cu2(μ-OAc)}3- were obtained, respectively. On the other hand, if [SeFe3(CO)9]2- was treated with [Cu(CH3CN)4]BF4/dppm or dppe in varied ratios and different solvents, a series of copper-incorporated E-Fe clusters: (μ5-Se)Fe3(CO)9Cu2(μ-dppm)(L) (L = CH3CN, THF), SeFe3 -(CO)9Cu2(μ-dppe), {[SeFe3(CO)9]2Cu2(μ-dppe)}2-, and {[SeFe3(CO)8]
-Cu2(μ-dppm)(μ-dppm)} were produced.
The reactions of Se powder with Mn2(CO)10/KOH/MeOH solution in varied reaction condition were systematically studied. While Se powder reacted with 0.5 eq Mn2(CO)10 in 0.9 M KOH/MeOH solution for 1 hr to produce [Se10Mn6(CO)18]4-, the similar reaction in 4 M KOH/MeOH solution gave [Se2Mn3(CO)9]2-. In the case of Se: Mn in the ratio of 10: 6, the reaction of Se with Mn2(CO)10 in 0.9 M or 4 M of KOH/MeOH for 1 hr led to formation of the new complex [Se10Mn6(CO)18]4-. However, if the reactions proceeded for ten days in 0.9 M and 4 M of KOH/MeOH solutions for ten days, [Se5Mn4(CO)12]2- and [Se6Mn6(CO)18]4- were obtained, both of which represent novel types of complexes in the Se-Mn-CO system.
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