| 二氰氨根[N(CN)2-]/三氰甲根[C(CN)3-]桥联双核钌RuⅡRuⅢ混合价配合物的设计合成、表征和电子传递行为 |
| Designed Syntheses, Characterization and Electron Transfer Behavior of RuⅡRuⅢ Mixed-valence Binuclear Ruthenium Complexes Bridged by Dicyanamide [N(CN)2-]/Tricyanomethanide [C(CN)3-] |
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| 摘要: trans-[XRu(py)4(NO)]2+(X=Cl，Br)与等物质的量的NaN3在甲醇中反应后生成中间体trans-[XRu(py)4(CH3OH)]+，它再与过量的Na[N(CN)2]或K[C(CN)3]反应后生成单核配合物trans-XRu(py)3L(X=Cl，Br，L=N(CN)2-，C(CN)3-)。单核配合物XRu(py)4L与[X′Ru(py)4(CH3OH)]+进行分子组装，生成了一系列双核钌配合物trans-[X(py)4Ru(μ-L)Ru(py)4X′]+。用等物质的量的NOBF4或(NH4)2[Ce(NO3)6]氧化这些RuⅡRuⅡ双核钌配合物，得到了一系列RuⅡRuⅢ混合价配合物trans-[X(py)4Ru(μ-L)Ru(py)4X′]2+。N(CN)2-桥联的RuⅡRuⅢ混合价配合物在近红外区存在中等强度的吸收，起源于混合价态间的电荷跃迁(Intervalence Charge Transfer，简称为IVCT)，且其最大吸收波长随着溶剂极性的改变而发生变化，它们属于Class Ⅱ类型的混合价化合物；而C(CN)3-桥联的RuⅡRuⅢ混合价配合物在近红外的吸收要强得多，且溶剂极性的改变对IVCT最大吸收波长基本无影响，它们属于介于价态定域与离域之间的混合价配合物。 |
| 关键词: 钌 混合价配合物 电子传递 电荷跃迁 二氰氨根 三氰甲根 |
| 基金项目: |
| Abstract: Reaction of trans-[XRu(py)4(NO)]2+(X=Cl, Br) with equimolar NaN3 in methanol produced intermediate trans-[XRu(py)4(CH3OH)]+, which reacted with Na[N(CN)2] or K[C(CN)3] induced isolation of trans-XRu(py)4L(X=Cl, Br; L=N(CN)2-, C(CN)3-). Incorporation of mononuclear complexes XRu(py)4L with [X′Ru(py)4(CH3OH)]+ afforded a series of binuclear ruthenium complexes trans-[X(py)4Ru( μ-L)Ru(py)4X′]2+. Oxidation of these RuⅡRuⅡ binuclear ruthenium complexes by addition of equimolar NOBF4 or (NH4)2[Ce(NO3)6] induced formation of a series of RuⅡRuⅢ complexes trans-[X(py)4Ru(μ-L)Ru(py)4X′]2+ with mixed-valence. For N(CN)2-bridged RuⅡRuⅢ mixed-valence complexes, a moderate absorption occurs in the near infrared region originating from intervalence charge transfer (IVCT) transition. Their IVCT absorption maximums show an obvious shift with the change of solvent polarity, characteristic of Class Ⅱ mixed-valence compounds. By contrast, C(CN)3-bridged RuⅡRuⅢ mixed-valence complexes afford a much stronger absorption in the near-infrared region. Their IVCT absorption maximums are insensitive to the solvent polarity, suggesting that they belong to borderline compounds between valence-trapped and -untrapped. CCDC: 611846, 3; 611847, 4; 611848, 5·H2O; 611849, 6; 611850, 7·CH2Cl2; 611851, 8·2CHCl·1/2C2H4Cl2; 611852, 9·2CHCl3·1/2CH2Cl2; 611853, 10; 611854, 11·5/2CHCl3·H2O; 611855, 12·5/2CHCl2·H2O; 611856, 13·1/2CH2Cl2. |
| Keywords: ruthenium mixed-valence complex electron transfer charge transfer dicyanamide tricyanomethanide |
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| 张礼仪,诸月梅,施林熙,陈忠宁.二氰氨根[N(CN)2-]/三氰甲根[C(CN)3-]桥联双核钌RuⅡRuⅢ混合价配合物的设计合成、表征和电子传递行为[J].无机化学学报,2006,22(8):1453-1466. |
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