Abstract
The enthalpies and entropies of complexation of alkali and alkaline‐earth metal cations by several macrobicyclic ligands have been obtained from calorimetric measurements and from the previously determined stability constants [2]. Both enthalpy and entropy changes play an important role in the stability and selectivity of the complexes. Particularly noteworthy are the large enthalpies and the negative entropies of complexation obtained for the alkali cation complexes (Na^+^, K^+^, Rb^+^ and Cs^+^ cryptates). The Sr^2+^ and Ba^2+^ as well as [Li^+^ ⊂ 2.1.1]For use of the symbols see [2].
and [Na^+^ ⊂ 2.2.1] cryptates are of the enthalpy dominant type with also a favourable entropy change. The Ca^2+^ and [Li^+^ ⊂ 2.2.1] cryptates are entirely entropy stabilized with about zero heat of reaction. The high stability of the macrobicyclic complexes as compared to the macromonocylcic ones, the cryptate effect, is of enthalpic origin. The enthalpies of complexation display selectivity peaks, as do the stabilities, whereas the entropy changes do not. The high M^2+^/M^+^ selectivities found in terms of free energy, may be reversed when enthalpy is considered in view of the very different role played by the entropy term for M^2+^ and M^+^ cations. The enthalpies and entropies of ligation show that whereas the cryptate anions are similar in terms of entropy irrespective of which cation is included, the ligands, despite being more rigid than the hydration shell, are nevertheless able to adjust to some extent to the cation. This conclusion agrees with published X‐rays data. The origin of the enthalpies and entropies of complexation is discussed in terms of structural features of the ligands and of solvation effects.