Abstract
The new lithium-selective complexant 5,12,17-trimethyl-1,5,9,12,17-pentaazabicyclo[7.5.5]nonadecane (TMPAND) was used to synthesize Li+(TMPAND)Na−, the first alkalide prepared from an azacage complexant. This sodide was characterized by a variety of methods. Differential scanning calorimetry experiments showed a reversible, endothermic, solid-solid phase transition at an onset temperature of −75 ± 3°C and with ΔH = 3.3 ± 1 kJ/mol.23Na NMR spectra showed a peak at −61 ppm, characteristic of a sodium anion, and a second minor peak at −10 ppm, probably due to the interaction of Na- with trapped electrons. The quadrupole coupling constant of the complexed lithium cation was found to be 0.19 MHz at −100°C, and7Li NMR spectra showed a discontinuity in the line width of the7Li NMR peak and in the quadrupole coupling constant at the phase transition.
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This paper is dedicated to the memory of the late Dr C. J. Pedersen.
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Eglin, J.L., Jackson, E.P., Moeggenborg, K.J. et al. Li+(TMPAND)Na−: The first alkalide prepared from an azacage complexant. J Incl Phenom Macrocycl Chem 12, 263–274 (1992). https://doi.org/10.1007/BF01053867
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DOI: https://doi.org/10.1007/BF01053867