ISSN:
1573-1111
Keywords:
Crown ether
;
binding constants
;
polystyrene
;
networks
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The binding constants,K N, of sodium and potassium 8-anilinonaphthalene-1-sulfonate (ANS) and of sodium 5-dimethylamino-1-naphthalenesulfonate (DNS) to benzo-18-crown-6 bound to a 2% cross-linked polystyrene network (RN18C6) were measured spectrophotometrically in dioxane and the results compared with those obtained for picrate salts. The network RN18C6 was then used to measure in dioxane and toluene by a competition method the equilibrium constant,K, of the reaction A−M+N+Cr⇄A−M+Cr+N.A−M+N denotes the ionic solute (ANS, DNS, methyl orange or picrate salt) bound to the network RN18C6 (N) and A−M+Cr is the solute bound to a soluble ligand Cr, where Cr represents a series of 18-crown-6 and 15-crown-5 compounds. Combining theK N andK values the formation constants,K L, of the crown ether complexes of the respective salts were obtained in dioxane. The data show a reversal in the complexation strength of the 18-crown-6 compounds in dioxane when sodium picrate is replaced by sodium ANS. The results were rationalized in terms of a synergistic effect exerted by dioxane, with dioxane forming a 1:1 dioxanate with the crown ion pair complex. This effect is especially strong with ANS and with a rigid planar crown ether like dibenzo-18-crown-6. The binding constants,K N, of NaANS and NaDNS to RN18C6 in dioxane are nearly three times larger than for sodium picrate, and the same holds for the potassium salts. Differences in anion interactions with the network appear to be a plausible cause for the anion dependence ofK N.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00687993
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