研究生: |
林怡君 |
---|---|
論文名稱: |
含硒之鉻、鉬、鎢金屬及碲之鉻金屬羰基化合物的合成及反應性研究 |
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: | 2003 |
畢業學年度: | 91 |
語文別: | 中文 |
論文頁數: | 126 |
中文關鍵詞: | 金屬團簇化合物 、固氮酵素 |
英文關鍵詞: | metal clusters, nitrogenase |
論文種類: | 學術論文 |
相關次數: | 點閱:156 下載:0 |
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[1] 硒(Se)-鉻(Cr)、鉬(Mo)、鎢(W)的研究
將 [Se2Cr3(CO)10]2- 與1當量的W(CO)6在丙酮中加熱反應,可得混合鉻鎢金屬的化合物 [Se2Cr2W(CO)10]2-;若以過量的W(CO)6在丙酮中加熱反應,則可得開放結構化合物 [Se2W4(CO)18]2- 及雙三角錐封閉結構化合物 [Se2W3(CO)10]2-。
[Se2Cr3(CO)10]2- 與第七族的異核金屬 Mn(CO)5Br反應:在丙酮中反應,可得一結構特殊的混合鉻-錳金屬化合物 [Me2CSe2Cr2Mn(CO)14]-。
[Se2Mo3(CO)10]2- 與第八族的異核金屬Fe(CO)5於丙酮中反應,可得到具有cubic結構的化合物 [Se3Mo5(CO)9(=O){C(CH3)2CH2C(=O)CH3}]3-(主產物)和已知產物[SeFe3(CO)9]2-(副產物);與Ru3(CO)12反應則得到已知產物具八面體結構的化合物 [Se2Ru4(m-CO)4(CO)8]2-。[Se2W3(CO)10]2- 與第八族的異核金屬Fe(CO)5反應則得到已知產物 [SeFe3(CO)9]2-。
[2] 碲(Te)-鉻(Cr)系統的研究
將Te與Cr(CO)6以1:3的比例在鹼性甲醇溶液中反應,再加入Et4NBr則可得黃褐色化合物 [Et4N]2[Te{Cr(CO)5}3]。不同於 [Te{Cr(CO)5}2]2-,此產物於MeOH溶液中可穩定存在。
[Te{Cr(CO)5}2]2- 與第八族的異核金屬Fe(CO)5、Ru3(CO)12反應,皆得到氧化性產物 [Te{Cr(CO)5}3]2-,而在與Ru3(CO)12的反應,另外可得一具四面體結構之化合物 [TeRu3(CO)9]2-。[Te{Cr(CO)5}2]2- 與HBF4反應可生成一質子化產物 [HTe{Cr(CO)5}2]-;於CH3CN溶液中加熱,則可得到一乙基化產物 [EtTe{Cr(CO)5}2]-;另外與Cr(CO)6反應,則成功合成出 [Te{Cr(CO)5}3]2-。
[1] Se-Cr system
Refluxing [Se2Cr3(CO)10]2- with 1 equiv. of W(CO)6 in acetone yields the W-substituted dichromium cluster [Se2Cr2W(CO)10]2-. On the other hand, refluxing [Se2Cr3(CO)10]2- with excess W(CO)6 in acetone leads to formation of the arachno-cluster [Se2W4(CO)18]2- and the closo-cluster [Se2W3(CO)10]2-. When [Se2Cr3(CO)10]2- was treated with Mn(CO)5Br in acetone at room temperature, the unusual mixed-metal cluster [Me2CSe2Cr2Mn(CO)14]- was produced.
Reaction of [Se2Mo3(CO)10]2- with Fe(CO)5/KOH forms the cubane-like cluster [Se3Mo5(CO)9(=O){C(CH3)2CH2C(=O)CH3}]3- and the known compound [SeFe3(CO)9]2-. While treatment with Ru3(CO)12 produces the known octahedral complex [Se2Ru4(m-CO)4(CO)8]2-, the reaction of [Se2W3(CO)10]2- with Fe(CO)5/KOH yields the known compound [SeFe3(CO)9]2-.
[2] Te-Cr system
Reaction of Te powder with Cr(CO)6 in a molar ratio of 1:3 in basic methanol solution produces [Et4N]2[Te{Cr(CO)5}3] by the addition of Et4NBr. Unlike [Te{Cr(CO)5}2]2-, this species is stable in methanol solution at room temperature.
Whereas [Te{Cr(CO)5}2]2- was treated with Fe(CO)5 to form [Te{Cr(CO)5}3]2-, the treatment with Ru3(CO)12 affords [Te{Cr(CO)5}3]2- and the tetrahedral cluster [TeRu3(CO)9]2-. [Te{Cr(CO)5}2]2- can further be protonated with HBF4 to form the monohydrido complex [HTe{Cr(CO)5}2]-. Interestingly, [Te{Cr(CO)5}2]2- in refluxing CH3CN leads to ethylated complex [EtTe{Cr(CO)5}2]-. In addition, the reaction of [Te{Cr(CO)5}2]2- with Cr(CO)6 gives the oxidizing product [Te{Cr(CO)5}3]2-.
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