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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 27 (1997), S. 155-168 
    ISSN: 1573-1111
    Keywords: Dicarboylated calix[4]arenes ; sodium and potassium complexes ; solvent extraction ; selectivity ; 1H-NMR mononuclear and dinuclear species
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The extraction of sodium and potassium ions by 25,27-dicarboxymethyl-26,28-dimethoxy-5,11,17,23-tetra-tert-butyl calix[4]arene (L1H2) in chloroform shows the formation of MLIH and M2LI complexes (M = Na, K). In 1,2-dichloroethane, the MLIH species are formed in the acidic pH range, while only the Na2LI species is found at high pH values. The corresponding extraction equilibrium constants K11 (M) and K21 (M) have been evaluated and show a selectivity in favour of Na+ as compared to K+, whatever the nature of the complexes. In chloroform, this selectivity is much more pronounced considering the 2 : 1 complexes: K11(Na)/K11(K)≪ K21(Na)/K21(K). The coexistence of 1 : 1 and 2 : 1 metal : ligand complexes is also shown in the extraction of sodium in 1,2-dichloroethane by the 25,27-dicarboxymethyl-26,28-dimethoxyethoxy-5,11,17,23-tetra-tertbutyl calix[4]arene (LIIH2), locked in the cone conformation. Structural data of the complexes are discussed on the basis of 1H-NMR spectra. In particular, for LIH2, a conformational change from cone to partial cone upon metal complexation has been evidenced for the complexes KLIH, K2LI and Na2LI.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 22 (1995), S. 107-117 
    ISSN: 1573-1111
    Keywords: p-tert-Butylcalix[4]arene ; crown ethers ; alkali ions ; liquid-liquid extraction ; synergistic effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mixtures of macrocyclic crown ethers (L′=DC18C6, DB18C6, 18C6; L″=B15C5) andp-tert-butylcalix[4]arene (LH4) in dichloroethane exhibit synergistic effects in the extration of alkali ions (M+). These extractions are described by two independent reactions: —a two phase ion exchange: $$LH_{4org} + M_{aq}^ + \rightleftharpoons MLH_{3org} + H_{aq}^ + , (K_{ex} )$$ —the formation of an adduct in the organic phase: $$MLH_{3org} + nL_{org}^\prime (or nL_{org}^{''} ) \rightleftharpoons LH_3 ML_{norg}^\prime (or LH_3 ML_{norg}^{''} )(K_{fn} ).$$ It is shown thatn=1 for all the systems including 18 membered crown ethers (M=Na, K, Rb, Cs) and for the Na+-B15C5 system; whereasn=2 in the case of the K+-B15C5 and Rb+-B15C5 systems. Ion size effects on the stability constant of the adducts reveal strong interactions between the crown ether and the cation in the above mentioned systems. The corresponding adduct in the Cs+—B15C5 system has a very low stability constant in comparison with the others. This seems to show that B15C5 is unable to remove the Cs+ ion from the calixarene ‘cup’ in the cesium calixarenate complex.
    Type of Medium: Electronic Resource
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