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含硒與碲之釕金屬團簇化合物的合成與其反應探討及其他相關之研究

By [[author]]賴韻文, [[author]]Yun-Wen Lai, 賴韻文 and Yun-Wen Lai

Abstract

[[abstract]]1. E-Ru-CO (E = Te, Se) System When K2TeO3 was treated with 1 equiv of Ru3(CO)12 in methanol at 70 °C, the octahedral cluster [PPh4]2[TeRu5(CO)14]·CH2Cl2 was obtained in good yield. If K2TeO3 was treated with 2/3 equiv of Ru3(CO)12 in methanol at 80 °C, the unique high-nuclearity cluster [PPh4]2[Te4Ru8(CO)19] was obtained, which contains three novel m5-Te ligands. [PPh4]2[TeRu5(CO)14]·CH2Cl2 could transform to [PPh4]2[Te4Ru8(CO)19] upon the reaction with excess K2TeO3 in methanol at 80 °C. On the other hand, when K2SeO3 was treated with 5/3 equiv of Ru3(CO)12 in methanol at 70 °C, the octahedral cluster [PPh4]2[SeRu5(CO)14]·CH2Cl2 was produced. Further, the reaction of K2SeO3 with 2/3 equiv of Ru3(CO)12 in methanol at 70 °C formed the hydride-bridged octahedral complex [PPh4][HSe2Ru4(CO)10]. 2. E-Ru-Cu (E = Te, Se) System A series of novel octahedron-based E-Ru-Cu (E = Te, Se) cluster complexes, [ERu5(CO)14CuX]2-, [ERu5(CO)14(CuX)2]2-, [E2Ru4(CO)10- (CuX)2]2-, and [E2Ru10(CO)28Cu4X2]2- was produced from the reactions of [ERu5(CO)14]2- with CuX (X = Cl, Br, I). If [TeRu5(CO)14]2- was treated with [Cu(MeCN)4][BF4] in different ratios, the copper-incorporated Te-Ru-CO clusters, [Te2Ru10(CO)28- Cu3Cl]2- and TeRu5(CO)14(CuNCMe)2, were produced. Solvent-induced isomerization of TeRu5(CO)14(Cu-NCMe)2 was observed, which was supported by DFT calculation. The first ternary Te-Ru-Cu cluster, the chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}?, was discovered from the reaction of K2TeO3 with Ru3(CO)12 in MeOH followed by the addition PPh4Br and CuCl. This infinite chain possesses the semiconducting property with a low band gap of approximately 0.37 eV. 3. Se/Ru/CO Clusters in the Alcohol System We have synthesized a series of double-octahedron clusters [Se4Ru10(CO)24(O2COMe)]3-, [Se4Ru10(CO)24(O2CMe)]3-, and [Se4Ru10(CO)24(O2CEt)]3- from the reaction of SeO32- with Ru3(CO)12 in alcohol solutions. The X-ray analysis shows that [Se4Ru10(CO)24(O2COMe)]3- and [Se4Ru10(CO)24(O2CMe)]3- each display two Se2Ru4(CO)10 octahedra linked by the Ru2(CO)4 group which is further bridged by the O2COMe or O2CMe group. Interestingly, when [SeRu5(CO)14]2- was refluxed in MeOH under an atmosphere of CO2, the O-H activation and CO2 insertion product [Se4Ru10(CO)24(O2COMe)]3- was obtained.

Topics: 金屬團簇化合物, 硒, 碲, 釕, Metal Cluster, Se, Te, Ru, [[classification]]39
Year: 2010
OAI identifier: oai:ir.lib.ntnu.edu.tw:309250000Q/2867
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