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Extra info for Alkali Metal Complexes with Organic Ligands

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In macrobicyclic complexes, the ligand may exist in three forms differing by the configuration of the bridgehead nitrogens: exo-exo (x-x), exo-endo (x-n) and endo-endo (n-n) (or out-out, out-in and in-in respectively (727)) (see Figure 8). These forms may interconvert rapidly via nitrogen inversion. 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.

The overall process is represented b y equation (X). Conformational changes m a y occur. Bimolecular processes might contribute, especially in solvents of low polarity (see, however, 143). A limited number of exchange rates have been reported, based mainly on NMR data (Table 13). Exchange kinetics are of prime importance in transport processes, where, however, more complex mechanisms may be operative t h a n in the systems described here (see below andp. 145). Although the measurements do not all refer to the same solvent, some characteristic features m a y be extracted from the data.

M. Lehn complexes formed b y macrocyclic I 5 or natural ligands. The rates and free energies of activation for dissociation follow the same sequence as the stability constants. e. from Li+ to Cs+ and from Ca2+ to Ba2+ (744). 2. All association rates are much slower than a diffusion controlled process, which would have a rate of about 109 M -1 sec -1 (13d). However, the rates and free energies of activation seem to v a r y less from one system to another for the association than for the dissociation process.

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Alkali Metal Complexes with Organic Ligands by J. D. Dunitz

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