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Additional info for Alkali Metal Complexes with Organic Ligands
The reaction product should be insensitive to the reaction conditions, since high dilution is usually maintained via slow addition of the reactants at the expense of reaction duration. 28 Design of Organic Complexing Agents. Strategies towards Properties Nature o/the "bridgeheads". The "bridgehead" atoms are the atoms corresponding to the vertices of degree 3 in systems A - - J (Figure 2). Although any atom of valence three or higher can occupy these positions, carbon and nitrogen are the most important ones.
If the ligand is rigid, both distortions may cause marked destabilization. 2]. However a given selectivity may be increased by structural modifications. For instance the K+/Rb + selectivity increases markedly from 80 to 86. Indeed the introduction of the benzo ring is expected to decrease the cavity size (shorter 0 . . 0 distance) and to increase ligand rigidity (rotation about the central C--C bond in the benzo bridge is frozen). Both effects hinder the cavity dilatation required for Rb + inclusion; on the other hand, they also favour the smaller Na + cation with respect to K+, thus diminishing the K+/Na + selectivity of 36 as compared with 80.
Both effects hinder the cavity dilatation required for Rb + inclusion; on the other hand, they also favour the smaller Na + cation with respect to K+, thus diminishing the K+/Na + selectivity of 36 as compared with 80. 2. Con/ormational changes of the ligand on complexation may occur if the ligand has enough flexibility. Among macrocyclic ligands, particularly high K+/Na+ selectivities are found for the decapeptide valinomycin and the synthetic decaether 19 (Table I l). Both compounds are flexible molecules which undergo conformational changes on complexation, by wrapping around the complexed cation.