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  • 1975-1979  (2)
  • 1975  (2)
  • Organic Chemistry  (2)
  • Molecular Cell Biology
  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 12,12-Dimethyl-1,4,7,10-tetraazacyclotridecane (I), 11,13-dimethyl-1,4,7,10-tetraazacyclotridecane (II), 11,11,13-trimethyl-1,4,7,10-tetraazacyclotridecane (III) and 1,4,7,10,12,12-hexamethyl-1,4,7,10-tetraazacyclotridecane (IV) have been synthesized and their properties are described.While the Ni2+ and Cu2+ complexes of I-III have square planar geometries, those of IV are pentacoordinate according to their absorption spectra. Similarly, while the Co2+ complex of I is octahedral and readily oxygenated, the analogous complex with IV is pentacoordinate and not sensitive to oxygen.The rate of complexation of these ligands with Cu2+ and Ni2+ decreases in the order I 〉 II 〉 III ≫ IV, indicating that the number as well as the position of the methyl groups are important. Finally for Cu2+ the formation of the thermodynamic stable end product is slown down by methyl substitution in α-position to the coordinating nitrogen atoms (ligand II and III) so that an intermediate can be observed, whereas with I Cu2+ directly forms the end product.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 58 (1975), S. 1881-1886 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability constants of the Ni2+ and Co2+ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H2DACODA) have been determined potentiometrically in 0.5M KNO3 at 25°. Only M(DACODA) and M(DACODA)OH- were observed.In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law vf = kf [M2+] [HDACODA-]/[H+], which can be interpreted as a bimolecular process either between M2+ and DACODA2- (kM,LML) or between MOH+ and HDACODA- (kMOH,HLML). The second order rate constants kM,LML are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH+ and HDACODA- as reactive species. The dissociation rate is given by vd = (kML + kHML [H+]) · [M(DACODA)].
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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