Heterodinuclear Metal Arrangement in a Flat Macrocycle with Two Chemically- Equivalent Metal Chelating Sites

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• 作者：Masumi Kuritani ; Shohei Tashiro ; Mitsuhiko Shionoya
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：February 6, 2012
• 年：2012
• 卷：51
• 期：3
• 页码：1508-1515
• 全文大小：486K
• 年卷期：v.51,no.3(February 6, 2012)
• ISSN：1520-510X

文摘

A phenanthroline-based macrocycle 1 has been newly developed which has two chemically equivalent metal chelating sites within the spatially restricted cavity for dinuclear metal arrangement. The macrocycle 1 reacts with Zn(CF₃CO₂)₂ or ZnCl₂ to form homodinuclear Zn(II)-complexes. A single-crystal X-ray structural analysis of the resulting Zn₂1(CF₃CO₂)₄ determined the complex structure in which two Zn(II) ions are bound by two phenanthroline sites and two CF₃CO₂^{鈥?/sup> ions bind to each Zn(II) ion in a tetrahedral geometry. Similarly, a homodinuclear Cu(I)-macrocycle was formed from 1 and Cu(CH₃CN)₄BF₄. Notably, from 1 and an equimolar mixture of Cu(CH₃CN)₄BF₄ and Zn(CF₃CO₂)₂, a heterodinuclear Cu(I)鈥揨n(II)-macrocycle was exclusively formed in high yield (>90%) because of the relatively low stability of the dinuclear Cu(I)-macrocycle. A heterodinuclear Ag(I)鈥揨n(II)-macrocycle was similarly formed with fairly high selectivity from a mixture of Ag(I) and Zn(II) ions. Such selective heterodinuclear metal arrangement was not observed with other combinations of M-Zn(II) (M = Li(I), Mg(II), Pd(II), Hg(II), La(III), and Tb(III)).}