Cryptands cavity size

The match between crown cavity diameter and cation diameter is obvious from Table 3 showing that, eg, and 12-crown-4 (la) or, respectively and 18-crown-6 (Ic) correspond. Similar are the cryptands of gradually increasing cavity size [2.1.1], [2.2.1] and [2.2.2] for and... 

The parent series of cryptands may be represented by (213) - a stepwise increase in cavity size occurs along this series. High-dilution procedures are employed for the synthesis of these cages. 

Cryptands of the type (217)-(220) tend to form stable complexes with a number of heavy metal ions. Of particular interest is the selectivity of (219) for Cd(n) the complex of this metal is approximately 106-107 times more stable than its complexes with either Zn(n) or Ca(n). This reagent may prove useful for removing toxic Cd(n) from biological systems as well as for other applications involving sequestration of this ion (for example, in antipollution systems). The selectivity observed in the above case appears to arise because (i) the nitrogen sites favour coordination to Zn(n) and Cd(n) relative to Ca(n) and (ii) the cavity size favours coordination of Cd(n) relative to Zn(n). 

Complexation constants of crown ethers and cryptands for alkali metal salts depend on the cavity sizes of the macrocycles 152,153). ln phase transfer nucleophilic reactions catalyzed by polymer-supported crown ethers and cryptands, rates may vary with the alkali cation. When a catalyst 41 with an 18-membered ring was used for Br-I exchange reactions, rates decreased with a change in salt from KI to Nal, whereas catalyst 40 bearing a 15-membered ring gave the opposite effect (Table 10)l49). A similar rate difference was observed for cyanide displacement reactions with polymer-supported cryptands in which the size of the cavity was varied 141). Polymer-supported phosphonium salt 4, as expected, gave no cation dependence of rates (Table 10). 

Figure 7.1.4. The scheme of formation of [2.2.2]cryptand. marked the start of molecular recognition studies. As described in Chapters 2 and 3, the Pedersen analysis was later extended by Lehn s studies of the complementarity of sizes and shapes ofthe cryptand cavities and their guests, and by Cram s preorganization studies. In general, crown ethers and cryptands exhibit analogous complexation behaviour. Thus, similarly to the former host molecules, cryptands in the free, uncomplexed state elongate the vacant cavity by rotating a methylene group inward. Thus, the N...N distance in [2.2.2]-cryptand 54 across the cavity is extended to almost 70 pm [18] whilst, in the complexed...

Fig. 18 Top-. Structures of alkali metal complexes of 2.2.2-crypt, 9 (hydrogen atoms omitted for clarity) 139—42. Bottom Torsion angles defined by the two triangles obtained by linking the two sets of three oxygen atoms. The smaller the torsion angle, the higher the distance between the two pivot nitrogen atoms (and the larger the cavity size of the cryptand)...

The hexaimino cryptand L44 (Fig. 38) is close to the lower limit of cavity size for a dinucleating ligand. A dinuclear copper (I) complex of... 

Cryptands are macro-bi- or -poly-cycles able to encapsulate an ion by providing it higher protection because of their cagelike structures, as in (147) and (148). For these ligands the correspondence between cavity size and complex stability is more pronounced than for simple crown ethers. Recent approaches to improve the metal-ion selectivity of cryptands, as for example by replacement of ethylene units between each donor atoms with propylene units, or by insertion of several substituents into the macrocycles, have been reviewed.245 A new, interesting family of cryptands is constituted by borocryptands (149), which are useful receptors for chiral substrates, where enantiomeric differentiation can be achieved by using NMR spectroscopy.246... 

Cryptands are cyclic (mainly) polyether molecules with usually three chains linked at nitrogen caps at each end of the molecule (Figure 4.42), much like the sarcophagines but with a different capping atom and different donors. They can, depending on host cavity size, bind metal ions (alkali or alkaline earth ions preferred) or small molecules. A wide range of molecules of this family have been prepared. They can be effective in metal ion selection from a group of ions, useful in both analysis and separation of mixtures. They also help solubilize metal ions in aprotic solvents. 

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