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By J. D. Dunitz

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Example text

Whereas the situation is far from clear in the ligand, the endo-endo form should be strongly favoured in the complex, since it allows both nitrogens to participate in complexation interactions. 2] (103) and of several [2]-cryptates showed that the cation was indeed contained in the tridimensional molecular cavity and that in aU cases the ligand was in the n-n form. 2, Ba ~'+] 2SCN- --2H~O (126). 2] and of its RbSCN cryptate. It is seen that the ligand is flattened and elongated when free, whereas it has swollen up in the complex.

Consequently, replacing oxygen sites by nitrogen sites should increase the Ag+/Na+, TI+/K+ selectivities. ~] (Table 11) (84). 6. Complexation Selectivity. 2] for Sr ~'+ (factor 4000) and for Ba ++ (factor l0 s} with respect to Ca 2+ (Table 11). At present, this seems to be the only case known of such a behaviour, which is to be related to the fact that 80 is a rigid neutral ligand of suitable cavity size to complex AEC's. If a charged ligand site were introduced, a shift towards the usual Ca 2+ > Ba 2+ stability sequence would be expected, since charge-charge interactions strongly favour small cations over large ones.

A major contribution to this increase may arise from stronger cation-ligand interactions and from the larger gain in entropy on removal of the solvation shell (see hydration entropies in Table 1). 2]). No data are available for detecting a macrocyclic effect; however, by comparing the Ba ++ complexes of 30 and 22 (as done above for K+), a macrobicyclic effect of about 104--105 may be estimated. The AEC complexes of the natural ligands are of comparatively low stability (see below). EnthaltSy]entropy contributions to the stability (and also to the selectivity) of the complexes may be separated using calorimetric data.

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