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  • 1
    ISSN: 1432-1327
    Keywords: Key words Platinum(II) ; Migration ; Oligopeptides ; Methionine ; Histidine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The pH- and time-dependent reaction of [Pt(dien)(H2O)]2+ with the methionine- and histidine-containing peptides H-His-Gly-Met-OH and Ac-His-Ala-Ala-Ala-Met-NHPh at 313 K has been investigated by HPLC and NMR spectroscopy. For both peptides, initial relatively rapid formation of the kinetically favoured methionine S-bound complex is followed by slow intramolecular migration of the [Pt(dien)]2+ fragment to imidazole Nε 2 (or, in the case of H-His-Gly-Met-OH, to a much lesser extent to the competing imidazole Nδ 1) of the histidine side chain over a period of 500 h. Time-dependent studies for the pentapeptide at pH 8.0 demonstrate that this isomerization can take place by either direct S→Nε 2 migration or by a two-step mechanism involving initial Nε 2 coordination of a second [Pt(dien)]2+ fragment and subsequent cleavage of the orginal Pt-S bond in the resulting dinuclear complex. The rate of κS/κN ε 2 isomerization is markedly reduced on lowering the pH to 5.1.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 505-507 
    ISSN: 1434-1948
    Keywords: Macrocycle ; Pyrazole ; N-Heterocycle ; Carbonate ; Copper ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 22-membered macrocycle, spanning four endocyclic pyrazole groups, viz. 1,4,9,14,17,22,27,28,29,30-decaaza-5,13,18,26-tetramethylpentacyclo[24.2.1.14,7.111,14.117,20]triacontane-5,7(28),11(29),12,18,20(30),24(27),25-octaene (22Pz), rendered the tetranuclear compound [Cu4(22Pz)2(CO3)2(MeOH)2](ClO4)4(MeOH)4. The copper(II) ions are in distorted octahedral N3O3 environments. All four pyrazole groups of each macrocycle participate in the coordination of the copper(II) ions. The cationic part of this compound is in fact a dimer of two macrocyclic ligands, each containing two copper(II) ions bridged by two carbonate ions in the highly unusual pentacoordinating fashion.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/98332_s.pdf or from the author.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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