含主族元素 (Se、Bi) 與過渡金屬 (Mn、Ru、Mo) 團簇化合物的合成與其反應探討及化性與物性研究

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2010

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1.Se─Ru─CuBr系統 [SeRu5(CO)14]2─ 可經由改變不同當量CuBr及不同條件下,可得一系列Se─Ru─Cu新穎化合物,單銅 [SeRu5(CO)14CuBr]2─、鄰邊雙銅 [SeRu5(CO)14(CuBr)2]2─、四銅 [Se2Ru10(CO)28Cu4Br2]2─ 和雙銅 [Se2Ru4(CO)10Cu2Br2]2─,這一系列化合物間存在有趣的轉換關係;進一步研究及其電化學和紫外/可見光光譜,利用理論計算來佐證實驗中所得到的結果,並探討CuBr對金屬核SeRu5 vs. Se2Ru4的影響,此外與以往Te─Ru─Cu化合物比較探討主族關係的影響。 2.Bi─Mo系統 利用 [Bu4N][BiMo3(CO)9(-OC2H4OMe)3Na] 與一系列金屬鹽類反應,生成 [Bu4N][BiMo3(CO)9(-OC2H4OMe)3ML] (ML = Li, Pb(NO3), Cd(OAc), Ca(OAc), HgCl2, ZnCl),而與Pb(OAc)2和Ca(MeCN)2試劑在MeOH溶劑下反應則分別得 {[[Bu4N][BiMo3(CO)9(-OMe)3Pb(OAc)]}2與[BiMo3(CO)9(-OC2H4OMe)3Ca(CH3CN)2]。進一步改以滴加不等當量的離子搭配紫外/可見光光譜,觀察陽離子捕捉和交換情形,此外對照原合成的實驗結果,討論離子進入對整個化合物的穩定性,再藉由TDDFT的理論計算探討其電子吸收能量躍遷形式。 3.Se─Mn系統 將化合物 [Se10Mn6(CO)18]4─ 與一系列含鹵素氧化性試劑反應。[Se10Mn6(CO)18]4─ 於CH2Cl2溶液下反應可得 [Se8Mn4(CO)12(CH)2]2─,若以MeCN為溶液與BrCH2CH2Br或碘進行反應,則生成化合物 [Se8Mn4(CO)12(Se)2]2─,而與CuCl反應,則得到未知之化合物及氧化性產物 [Se5Mn4(CO)12]2─,進一步探討化合物 [Se8Mn4(CO)12(CH)2]2─ 和[Se8Mn4(CO)12(Se)2]2─ 之間的結構轉換關係,並討論其電化學、光物理性質進行研究。
Abstract 1. Se─Ru─CuBr system When [SeRu5(CO)14]2─ was treated with various ratios of CuBr under different conditions, a series of Se─Ru─Cu clusters [SeRu5(CO)14CuBr]2─, [SeRu5(CO)14(CuBr)2]2─, [Se2Ru10(CO)28Cu4Br2]2─, and [Se2Ru4(CO)10Cu2Br2]2─ were obtained. In addition, the stepwise cluster transformation, electrochemistry, and photophysical properties of these CuBr-incorporated Se─Ru complexes were understood with the aid of DFT and TDDFT in terms of the effects of CuBr on the different metal cores, SeRu5 vs. Se2Ru4. The characteristics were further compered with the previously reported analogous Te─Ru─Cu carbonyl clusters. 2. Bi─Mo system The tetrahedral-like BiMo3-cluster [BiMo3(CO)9(-OC2H4OMe)3Na]─ with three pendant chelatig ligands (OC2H4OMe)3 which exibited the binding and exchanging characteristics for various metal ions, giving a series of corresponding clusters [BiMo3(CO)9(-OC2H4OMe)3ML]─ (ML = Li, Ca(MeCN)2, Ca(OAc), Pb(NO)3, ZnCl, Cd(OAc), HgCl2), [BiMo3(CO)9(-OMe)3Pb(OAc)]22─, and [BiMo3(CO)9(-OC2H4OMe)3Ca(CH3CN)2]. The ion-exchange processes and photophysical properties of the resultant products were also innestigated by UV-vis titrations which were further understood with TDDFT in terms of different metal fragments. 3. Se─Mn system When [Se10Mn6(CO)18]4─ was treated with CH2Cl2 in MeCN, the dianonic complex [Se8Mn4(CO)12(CH)2]2─ was formed. If [Se10Mn6(CO)18]4─ was treated with 1,2-dibromoethane or iodine in MeCN, [Se8Mn4(CO)12(Se)2]2─ could be obtained. In addition, [Se10Mn6(CO)18]4─ could react with CuCl to produce [Se5Mn4(CO)12]2─ and an unknown complex. Furthermore, the electrochemistry and photophysical properties of [Se8Mn4(CO)12(CH)2]2─ and [Se8Mn4(CO)12(Se)2]2─ were also studied.

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電化學, clusters, electrochemistry

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