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133Cs NMR Study of Cs+ Ion Complexes with Aza-18-crown-6, Diaza-18-crown-6 and Dibenzyldiaza-18-crown-6 in Binary Acetonitrile–Nitromethane Mixtures

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Abstract

Cesium-133 nuclear magnetic resonance spectroscopy was used as a sensitive probe to investigate the stoichiometry and stability of Cs+ ion complexes with aza-18-crown-6 (A18C6), diaza-18-crown-6 (DA18C6) and dibenzylediaza-18-crown-6 (DBzDA18C6) in different binary acetonitrile–nitromethane mixtures. In all cases, the exchange between free and complexed cesium ion was fast on the NMR time scale and only a single population average resonance was observed. The 133Cs chemical shift–mole ratio data indicated that the cesium ion forms 1:1 cation–ligand complexes with the investigated aza-crowns in all acetonitrile–nitromethane mixtures. The formation constants of the resulting complexes were evaluated from computer fitting of the chemical shift–mole ratio data. The stability of the resulting 1:1 complexes with Cs+ were found to vary in the order A18C6 > DBzDA18C6 > DA18C6. In all cases, there is the inverse relationship between the complex stability constants and the amount of acetonitrile in the mixed solvent.

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Authors and Affiliations

  1. Department of Chemistry, Razi University, Kermanshah, Iran

    Mojtaba Shamsipur

  2. Teacher Training University, Tehran, Iran

    Nastaran Sohrabi Gilani & Mohammad Kazem Rofouei

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  1. Mojtaba Shamsipur
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  2. Nastaran Sohrabi Gilani
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  3. Mohammad Kazem Rofouei
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Correspondence to Mojtaba Shamsipur.

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Shamsipur, M., Gilani, N.S. & Rofouei, M.K. 133Cs NMR Study of Cs+ Ion Complexes with Aza-18-crown-6, Diaza-18-crown-6 and Dibenzyldiaza-18-crown-6 in Binary Acetonitrile–Nitromethane Mixtures. J Solution Chem 40, 40–47 (2011). https://doi.org/10.1007/s10953-010-9625-7

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