含十六族元素(硒、碲)與第八族(釕)金屬團簇化合物的合成與其反應探討及化性研究

朱晏頤(Yan-Yi Zhu)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(2006年)

摘要

1. Se-Ru-CO 化合物之合成

將K2SeO3與Ru3(CO)12以原子比Se：Ru = 1：5的比例於MeOH下加熱反應，可得到化合物[SeRu5(CO)14]2-，若將原子比改為Se：Ru = 1：2，置於相同的反應條件下，可得到化合物[HSe2Ru4(CO)10]-；此外，若同樣以原子比為Se：Ru = 1：2，但在更高溫下反應則會得到更多核的化合物[Se4Ru6(CO)12]2-，因此可藉由調整起始物的比例及溫度，控制不同結構的化合物生成。

2. [HSe2Ru4(CO)10]-和[SeRu5(CO)14]2-與CO及CO2反應

化合物[HSe2Ru4(CO)10]-在MeOH下與CO加熱反應一段時間後，再外加Ru3(CO)12，可得到活化C-O鍵並伴隨CO嵌入的綠色化合物[{HSe2Ru4(CO)10}2(Ru2(CO)4)(O2CMe)]3-；而化合物[SeRu5(CO)14]2-在MeOH下與CO2加熱反應，則會得到活化O-H鍵及CO2插入的另一個綠色化合物[{HSe2Ru4(CO)10}2(Ru2(CO)4)(O2COMe)]3-。由此可見Se-Ru-CO的金屬團簇化合物具獨特的活化特性。

3. E-Ru-CuX (E = Te，Se) 的電化學研究

八面體的化合物[ERu5(CO)14]2- (E = Se、Te)與CuX (X = Cl，Br，I)在不同比例下反應，可以得到具有單銅蓋接[ERu5(CO)14CuX]2-及雙銅橋接[E2Ru4(CO)10(CuX)2]2-化合物，而此系列化合物在電化學上均具有氧化還原性質，DFT理論計算顯示此類化合物的HOMO主要貢獻在Ru原子及CuX，而LUMO則主要來自Ru原子的貢獻，與我們在電化學所偵測的氧化還原結果相符合。

關鍵字

釕 ； 金屬團簇化合物 ； 硒 ； 碲

並列摘要

1. Synthsis of Se-Ru-CO Clusters

When K2SeO3 was treated with 5/3 equiv of Ru3(CO)12 in methanol at 80 ?C, [SeRu5(CO)14]2- was obtained in good yields. If K2SeO3 was treated with 2/3 equiv of Ru3(CO)12 in methanol at 75 ?C, another octahedral cluster [HSe2Ru4(CO)10]- could be obtained. Further, if K2SeO3 was treated with 2/3 equiv of Ru3(CO)12 in methanol at higher temperature (> 100 ?C), the higher nuclearity cluster [Se4Ru6(CO)12]2- was formed.

2. Reactions of [HSe2Ru4(CO)10]- and [SeRu5(CO)14]2- with CO or CO2 in MeOH

The green cluster [{HSe2Ru4(CO)10}2(Ru2(CO)4)(O2CMe)]3- was obtained from the reaction of [HSe2Ru4(CO)10]- with CO followed by the addition of Ru3(CO)12 in refluxing methanol. This reaction not only involved with the C-O bond activation of MeOH, but also accompanied with CO insertion. However, if [SeRu5(CO)14]2- was treated with CO2 in refluxing methanol for several hours, another green cluster [{HSe2Ru4(CO)10}2(Ru2(CO)4)(O2COMe)]3- was formed. This reaction involved with CO2 insertion to the O-H bond of MeOH.
3. Electrochemical measurements of complexes E-Ru-CuX (E = Se, Te, X = Cl, Br, I)

A series of octahedral E-Ru-CuX cluster complexes, [SeRu5(CO)14CuX]2- and [E2Ru4(CO)10Cu2X2]2-, was produced from the reactions of [ERu5(CO)14]2- with CuX (X = Cl, Br, I), respectively. These clusters revealed rich oxidative and reductive properties by cyclic voltammetry measurements. In addition, the HOMOs of all these clusters were mostly localized around the Ru atoms and CuX, and the LUMOs were mostly localized around the Ru atoms. This environment is consistent with their electrochemical reduction or oxidation potentials.

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