Abstract
Calorimetric titrations have been performed in anhydrous acetonitrile at 25 °C to give the complex stability constants (Ks) and the thermodynamic parameters for the stoichiometric 1:1 complexation of light lanthanoid(III) nitrates (La−Gd) with N-methoxyethylaza-4,7,11,14-tetraoxacyclohexadecane (aza-16-crown-5 lariat) (1). Using the present and reported data, the complexation behavior of C- and N-pivot lariats with 16-crown-5 skeletons is discussed comparatively and globally from the thermodynamic point of view. Possessing structural flexibility as compared with lariat ether 15-(2,5-dioxahexyl)-15-methyl-1,4,7,10,13-pentaoxacyclohexadecane (16-crown-5 lariat) (2), aza-16-crown-5 lariat gave the highest Ks for Nd3+ among the light lanthanoid nitrates. The complex stability sequence as a function of reciprocal ionic diameter of lanthanoid showed a characteristic peak profile at Nd3+ for 1, the relative cation selectivity for Nd3+ over the neighboring Pr3+ and Sm3+ amounted to 9. Thermodynamically, the compl...
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