Abstract
Proton NMR was used to study the complexation reaction between silver ion and hexathia-18-crown-6 in a number of binary mixed solvents of dimethyl sulfoxide with acetonitrile and methanol. Formation constants for the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. The influence of solvent composition on the stability of the resulting complex is discussed. The exchange kinetics of Ag+-hexathia-18-crown-6 in 70-30 wt.% dimethyl sulfoxide-acetonitrile and 75-25 wt.% dimethyl sulfoxide-methanol were studied by proton NMR line-shape analysis. In both solvent mixtures, the exchange of thiacrown ether between the free and complexed sites was found to proceed via a dissociative pathway. The exchange rates and the activation parameters E a, Δ H ‡, Δ S‡, and Δ G‡ for the ligand exchange were determined and the influence of solvent properties on these parameters discussed.
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Shamsipur, M., Talebpour, Z. & Alizadeh, N. NMR Study of the Stoichiometry, Stability, and Ligand Interchange of Silver Ion-Hexathia-18-crown-6 Complex in Binary Dimethyl Sulfoxide Solvent Mixtures at 300 K. Journal of Solution Chemistry 32, 227–238 (2003). https://doi.org/10.1023/A:1022934317551
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DOI: https://doi.org/10.1023/A:1022934317551