Stability constants and derived Gibbs energies and enthalpies and
entropies of complexation of alkali−metal
cations and macrocycles (18-crown-6 and ethyl
p-tert-butylcalix(6)arenehexanoate) in
benzonitrile at 298.15
K derived from titration calorimetry (macro and micro) are first
reported. These data are compared with
those previously reported for cryptand 222 and these cations in this
solvent. A “peak” selectivity is observed
for the complexation of the calix(6)arene ester and alkali
metal cations with a monotonic increase in stability
from lithium to potassium followed by a decrease from the latter to
rubidium. This behavior is analogous to
that shown for cation binding involving 18-crown-6 and cryptand 222.
Similar to the process of complex
formation involving these ligands, that involving the
calix(6)arene ester and these metal cations is
enthalpy
controlled with an exothermic maximum for the potassium cation.
Among the ligands considered,
thermodynamic data involving cation−calix(6)arene ester
interactions are characterized by a lower enthalpic
stability (less exothermic) and a more favorable entropy (except for
K+) than corresponding data involving
cryptand 222 or indeed 18-crown-6. These results are analysed in
terms of solute−solvent interactions reflected
on the solution thermodynamic data of the free and the complexed
electrolytes and the ligand in benzonitrile.
Standard enthalpies of solution of macrocycles and their sodium
and potassium salts in benzonitrile measured
calorimetrically are discussed in relation to (i) corresponding data
for the uncomplexed salts and (ii) previously
reported data for sodium and potassium cryptate salts in various
solvents. Enthalpies of coordination referred
to the process in the solid state for eighteen systems involving sodium
and potassium coronates, cryptates,
and calix(6)arenates are derived and whenever possible these
are discussed on the basis of (i) available X-ray
crystallographic data and (ii) the anion effect on the coordination
process.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.