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首页> 外文期刊>Chemistry: A European journal >Self-assembled organometallic [12]metallacrown-3 complexes [Review]
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Self-assembled organometallic [12]metallacrown-3 complexes [Review]

机译：自组装的有机金属[12] metallacrown-3配合物[综述]

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The reaction of [(arene)RuCl2](2) (arene = C6H6 cymene, C6H3Et3, or C6Me6) or [Cp*RhCl2](2) with 3-hydroxy-2-pyridone in the presence of Cs2CO3 gives trinuclear metallamacro-cyclic complexes. The self-assembly process was shown to be completely diastereoselective, and a racemic mixture of complexes with MRMRMR or MSMSMS (M = Ru, Rh) configuration was obtained. Plausible mononuclear intermediates of the formula [(arene)RuCl(C5H4NO2)] (arene = cymene, C6Me6) have been isolated and characterized. A structurally related trimer was synthesized by using [(cymene)RuCl2](2) and 3-acetamido-2-pyridone instead of 3-hydroxy-2-pyridone. The macrocycles were shown to be highly potent ionophores for Na+ and/or Li+ with negligible affinities for the larger cation K+. The selectivities of the receptors depend on the pi -ligand present: whereas the (C6H6)Ru- and (cymene)Ru complexes bind both Li+ and Na+, the (C6Me6)Ru-, (C6H3Et3)Ru-, and Cp*Rh complexes bind exclusively Li. For all receptors, the presence of alkali metal ions can be detected electrochemically: the peak potential is shifted by > 300 mV toward anionic potential upon binding. This behavior was utilized to detect Li+ and Na+ colorimetrically. Single crystal X-ray analyses have been carried out on eight complexes, four of which are bound to an alkali metal halide ion pair. Structural parameters, which affect the affinity and selectivity are discussed. A computational study on [{MX}[12]crown-3] complexes (M = Li, Na: X = Cl, Br, I) was performed in order to compare relevant bond lengths and angles of the energy-minimized structures with those of the organometallic receptors. [References: 112]
机译：在存在Cs2CO3的情况下，[（arene）RuCl2]（2）（芳烃= C6H6异丙苯，C6H3Et3或C6Me6）或[Cp * RhCl2]（2）与3-羟基-2-吡啶酮的反应产生了三核金属环复合体。该自组装过程显示出完全非对映选择性，并获得了具有MRMRMR或MSMSMS（M = Ru，Rh）构型的复合物的外消旋混合物。分离并表征了式[（亚芳基）RuCl（C5H4NO2）]（亚芳基=异丙苯，C6Me6）的单核中间体。通过使用[（cymene）RuCl2]（2）和3-乙酰氨基-2-吡啶酮代替3-羟基-2-吡啶酮合成了结构相关的三聚体。大环化合物显示出对Na +和/或Li +而言是高效离子载体，对较大阳离子K +的亲和力可忽略不计。受体的选择性取决于存在的pi-配体：而（C6H6）Ru-和（cymene）Ru络合物结合Li +和Na +，（C6Me6）Ru-，（C6H3Et3）Ru-和Cp * Rh络合物绑定李。对于所有受体，可以通过电化学方法检测到碱金属离子的存在：结合后，峰电位向阴离子电位偏移> 300 mV。该行为用于比色检测Li +和Na +。已经对八个络合物进行了单晶X射线分析，其中四个与碱金属卤化物离子对结合。讨论了影响亲和力和选择性的结构参数。为了比较[{MX} [12] crown-3]配合物（M = Li，Na：X = Cl，Br，I）的计算研究，以比较相关的键长和能量最小化结构的键长和角度有机金属受体。 [参考：112]

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