Crown ethers metal cation complexes

Three examples of supermolecules are shown. Figure 4a shows how an individual ringlike crown ether molecule consisting of (—CH2—CH2—0-)-groups, so-called [18]-Crown-6, can bind a metal cation K" in aqueous solution [14]. This crown ether binds substantially less other cations, such as Na+, and therefore the bonding is selective. On the other hand, Na+ can be bonded if the size of the crown ether is reduced to consist of 5 ethylene oxide moieties, [15]-Crown-5. The interaction in crown ether/metal cation complexes is based on steric and charge match. Crown... 

Ever since Petersen reported the complexing ability of the crown ether with alkali, alkaline earth and other cations, crown ether became a major subject for researchers. This is due to the fact that crown ether possesses the ability to form complexes with a variety of inorganic salts and also the ability to solubilize these salts in aprotic solvents The complexation between metal cation and crown ether is believed to involve ion-dipole interactions and therefore is similar in nature to ordinary solvation. In addition, crown ether/metal cation complexes can serve as catalysts in reactions involving ionic intermediates. Polymerization of diene with crown ether/metal cation complexes is a typical example of this subject, since this reaction involves ionic intermediates. The detailed information including a brief history, chemical properties of crown ether and its application in the anionic polymerization and copolymerization have been discussed. 

Crown ether Metal cation Ion-dipole Complex (cavitand) [K+([18] crown-6)]... 

A. Arnold et al. determined the crystal structure of the same crown ether 4-NaI complex (20), Since their estimated bond lengths were comparable to those predicted, the density functional method is believed to be applicable for crown ether - alkali cation complex. We attempted to apply MM2 and MNDO calculations for several crown ether-alkali metal cation complexes f27). Since the parameters for weak interactions between alkali metal cations and neutral donor atoms have not been optimized completely, these calculations sometimes gave results which differ from those in experiments. 

Sr2+ so well that it was selectively extracted from a bulk sample of a barium salt (Helgeson et al., 1973a). Binding constants for metal-cation complexes of 1,3-xylyl-crown ethers [66]—[69] carrying an additional carboxylate binding... 

FABMS has been used as a semiquantitative indication of the selectivity of receptors for particular guest metal cations (Johnstone and Rose, 1983). The FABMS competition experiment on [7] with equimolar amounts of the nitrates of sodium, potassium, rubidium and caesium gave gas-phase complex ions of ([7] + K)+ ion (m/z 809) and a minor peak ([7] + Rb)+ ion (m/z 855) exclusively. The relative peak intensities therefore suggested a selectivity order of K+ Rb+ Na+, Cs+, indicative of the bis-crown effect, the ability of bis-crown ether ligands to complex a metal cation of size larger than the cavity of a single crown ether unit, forming a sandwich structure. 

Lariat ethers of structure 8 were found to be selective toward Li ion and the lariat crown ether-Li+ complexes are more stable than the corresponding complexes with Na or K+, in methanol. Nevertheless, experiments conducted in aqueous solution showed that Na+ had a better complexation ability than the other two alkali metal cations. Hence, selective complexation of lariat crown ethers with cations changes with the solvent system this may be due in part to the difference in solvation between solvent and cation (Figure 9 f. ... 

Reaction of 175 with Cgg yields a hydroxy-functionalized fullerene that can be further derivatized. This hydroxy-fullerene was coupled with a porphyrine unit via a polyethyleneglycol-Hnker. This linker can be arranged similarly to a crown-ether to complex metal cations. Complexation is used to tune the distance between the porphyrin imit and the Cgg-moiety and thus tune the donor-acceptor properties of this porphyrin-fuUerene hybrid [177]. 

The effect of cation-complexing agents on the barium(II)-assisted basic ethanolysis of phenyl acetate has been looked at.184 Addition of various crown ethers yields ternary complexes of 1 1 1 crown-metal-ethoxide composition and a definite cation activation takes place. Cryptand 222 removes the catalytic activity. 

Crown ether is the other important class of phase-transfer catalysts which critically differs from the onium salt, in that the whole inorganic salt is transferred into the organic phase. The reaction modes described above can generally be accommodated in such crown ether-catalyzed reactions, simply by replacing the onium cation by a metal cation complex of crown ether. 

Another significant deviation from known rules has been observed in the rather low affinity of K+ with the 1,10-diaza crown 18-C-6 with only AG=10 kJ/mol (in methanol). It has been shown that the free energy of binding AG in crown ether and ciyptand complexes usually is an additive function of number and electron donicity of the host donor atoms which are in contact with the metal ion.[17] Molecular mechanics calculations suggest the reduced affinity with the diazacrown to be due to the N-lone pairs in pseudoaxial position, pointing away from the metal ion (Figure 4). This has led to experiments with the N-methyl substituted crown here the N-alkyl substituents would clash which each other inside the macrocycle, therefore a pseudoequatorial lone pair orientation towards the cation is enforced, and the stability of the complex indeed returns to the normal scale with an increase to 29.5 kJ/mol.[ 18]... 

Very similar results were obtained from the CV studies of ( )-38 and ( )-39, but the observed anodic shifts of the first redox couples upon complexation with K+ were smaller (50 mV for ( )-38 and 40 mV for ( )-39). The reduction of the anodic shift from 90 mV (in ( )-37) to 40 mV (in ( )-38) can be explained by an increasing average distance between the cation bound to the crown ether and the fullerene surface, as the addition pattern changes from trans-1, to trans-2, and to trans-3 [55], Additionally, the effects of different alkali- and alkaline-earth-metal ion salts on the redox properties of ( )-37 were investigated. As expected, all electrochemical data clearly demonstrate a much larger interaction between crown-ether-bound cations with the negatively charged than with the neutral fullerene core [55],... 

The forces of ion-dipole interactions are mostly the basis for complex formation in these systems. This fact probably helps explain the possibility of complex formation of crown-ethers with cations whose size is bigger than the ether s cavity. In this case, the sandwich structures are formed, or a considerable displacement (going out) of metal cations out of the plane of the oxygen donor atoms [571]. Opened O-containing crown-ether podands [575-578], for instance, 302 and 303, belong to this structural type ... 

Incidentally, C. J. Pedersen s first report on crown ethers and their complexes was published in the same year as the mechanism of the biological activity of valinomycin was clarified [2], Crown ethers are cyclic derivatives of polyethylene glycol of varying ring size, an example of which is also depicted in Figure 2.2.1. The structural relationship with the ionophores is clearly visible. It is thus not surprising that crown ethers also bind metal cations by coordination with the oxygen atoms [1, 3]. 

Fig. 8. Ferrocene bis amido aza crown ether 1 2 ligand alkali metal cation complexes.

Alkalides and electrides are stoichiometric salts containing alkali metal cations complexed by crown ethers. Charge balance is provided by the alkali metal anions (alkalides) or trapped electrons (electrides). Rb and Rb NMR has been used to study a number of mbidium alkalides, electrides and related compounds (Kim et al. 

Crown ethers and cryptands, complexes with metal cations 79AG613,... 

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