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  • 1
    ISSN: 1434-1948
    Keywords: Cobalt(III) complexes ; Tetrapodal pentadentate ligand ; Hydrolysis ; Kinetics ; Mechanism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multi-wavelength stopped-flow spectrophotometry was used to study the kinetics of base hydrolysis of the octahedral cobalt(III) complex CoLCl2+ (2), in which the tetrapodal pentadentate ligand L has an NN4 donor set and forms a square-pyramidal coordination cap [L = 2,6-bis(1′,3′-diamino-2′-methylprop-2′-yl)pyridine, 1]. The kinetic investigation, carried out at different temperatures, pressures and ionic strengths I, led to second-order kinetics, rate = kOH [2][OH-], with kOH = 0.139 ± 0.001 M-1s-1 (I = 0.1 M) and kOH = 0.0570 ± 0.0004 M-1s-1 (I = 1.0 M) at 298 K. The temperature and pressure dependence of kOH resulted in ΔH
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 25 (1986), S. 673-682 
    ISSN: 0570-0833
    Keywords: Reaction dynamics ; Coordination modes ; High-pressure chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to understand the dynamics of chemical reactions in general, detailed information on electronic, structural and kinetic properties is required. The key questions on how chemical reactions actually occur can in many cases only be answered in terms of information obtained from kinetic studies. In conventional kinetic studies of chemical reactions in solution, the variables usually selected include concentration, acidity, solvent, and temperature. In recent years, pressure has become an additional selected variable in such studies. It enables the measurement of the volume of activation and the construction of reaction volume profiles and thus assists in the elucidation of the underlying mechanism; it also completes the comprehension of reaction kinetics by adding another kinetic parameter that the suggested reaction mechanism must account for. Furthermore, the volume of activation is the only transition state property that can be correlated with the corresponding ground state property in an experimentally simple manner. In this paper, the insights so gained in our understanding of the dynamics of reactions involving coordination complexes will be presented. Such reactions are of fundamental interest to chemists since they often form the basis of catalytic, biological, environmental and energy related processes. Any additional information that will add to the understanding of the reaction dynamics is therefore of exceptional importance.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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