β-Nitro Derivatives of Germanium(IV) Corrolates
β-Nitro Derivatives of Germanium(IV) Corrolates
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DOI：
10.1021/ic801421a
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发表时间：
2008-12-15
影响因子：
4.6
通讯作者：
Paolesse, Roberto
中科院分区：
文献类型：
--
作者：
Mastroianni, Marco;Zhu, Weihua;Paolesse, Roberto
meso-triphenylcorolates锗（IV）与硝酸盐反应，以高产率得到相应的β-硝基取代的coroles。粗反应混合物的色谱分离能够分离μ-氧代二聚体沿着在锗中心金属离子的轴向位置带有羟基或甲氧基的相应单体。根据反应条件，可以获得单硝基或二硝基取代的络合物。在每种情况下，取代是高度区域选择性的，在不同的可能异构体中仅得到3-硝基或3，17-二硝基衍生物。五个合成的配合物进行了检查，通过循环伏安法和紫外-可见光谱电化学在二氯甲烷中，和二硝基μ-氧代二聚体的结构特征。
The reaction between germanium(IV) meso-triphenylcorrolates and nitrate salts affords the corresponding beta-nitro substituted corroles in good yield. Chromatographic separation of the crude reaction mixtures enables isolation of a mu-oxo dimer along with the corresponding monomers bearing a hydroxy or methoxy group at an axial position of the germanium central metal ion. Depending on the reaction conditions, mono- or dinitro substituted complexes can be obtained. The substitution is highly regioselective in each case, giving only the 3-nitro or 3,17-dinitro derivative among the different possible isomers. Five of the synthesized complexes were examined by cyclic voltammetry and UV-visible spectroelectrochemistry in dichloromethane, and the dinitro mu-oxo dimer is structurally characterized.