NDLI: Conductometric studies of thermodynamics of complexation of Li$^{+}$, Na$^{+}$ and K$^{+}$ ions with 4′,4″(5″)-di-tert-butyldibenzo-18-crown-6 in binary acetonitrile

Content Provider	Springer Nature Link
Author	Taghdiri, Mehdi Payehghadr, Mahmood Behjatmanesh Ardakani, Reza Eslami, Nargess
Copyright Year	2012
Abstract	The complexation reactions between 4′,4″(5″)-di-tert-butyldibenzo-18-crown-6 (DTBDB18C6) and Li$^{+}$, Na$^{+}$ and K$^{+}$ ions were studied conductometrically in different acetonitrile–nitromethane mixtures at various temperatures. The formation constants of the resulting 1:1 complexes were calculated from the computer fitting of the molar conductance-mole ratio data at different temperatures. At 20 °C and in nitromethane solvent, the stability of the resulting complexes varied in the order K$^{+}$ > Na$^{+}$ > Li$^{+}$. The enthalpy and entropy changes of the complexation reactions were evaluated from the temperature dependence of formation constants. It was found that the stability of the resulting complexes increased with increasing nitromethane in the solvent mixture. The TΔS° versus ΔH° plot of thermodynamic data obtained shows a fairly good linear correlation indicating the existence of enthalpy–entropy compensation in the complexation reactions. The ab initio studies calculated at B3LYP/6-31G level of theory, indicate the binding energy of complexes decreases with increasing cation size in the gas phase. In the solution phase, DTBDB18C6 preferentially forms complexes with the larger ions rather than the smaller ions because the solvation energies of the smaller ions are large enough to overcome and reverse the trends in gas phase complexation. The findings of this study suggest that the current understanding of the factors influencing the selectivity of metal ion complexation by crown ethers may be in need of revision.
Starting Page	375
Ending Page	383
Page Count	9
File Format	PDF
ISSN	13883127
Journal	Journal of Inclusion Phenomena and Macrocyclic Chemistry
Volume Number	77
Issue Number	1-4
e-ISSN	15731111
Language	English
Publisher	Springer Netherlands
Publisher Date	2012-11-08
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	4′,4′′(5′′)-Di-tert-butyldibenzo-18-crown-6 Li$^{+}$, Na$^{+}$ and K$^{+}$ complexes Conductance Stability Mixed solvent Ab initio Organic Chemistry Food Science Crystallography
Content Type	Text
Resource Type	Article
Subject	Chemistry Condensed Matter Physics Food Science

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