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Additional resources for Alkali Metal Complexes with Organic Ligands
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.
The stability constants also drop by several decades on replacing 0 by S (see the pairs 10128, Table 8 andSO]89, Table 9). In addition to an electrostatic effect (Table3), a slight decrease of cavity size, due to the larger radius of an S site, may also play a role in this case. An opposite stability trend N > S > 0 may be expected (7,t0) -- and is found -- when the cation-ligand bond has appreciable covalent character as in the case of Ag+ ... N, Ag+ ... S interactions (compare data for the Ag+ complexes of ligands 10, 21 and 28 in Table 8).
Since the exchange rates are expected to be much slower within the organic membrane phase than in water, the hydrophilicity] lipophilicity balance of the carrier will also influence the transport rates; it determines the distribution of the complex between the two phases and affects the interface processes. The design of a s~eeific cation carrier thus presents two main additional requirements: lipophilicity and a compromise between thermodynamics and kinetics of complexation. Some lipophilicities calculated from the parameters of Hansch (Table 5) are listed in Table 12.