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  • 1
    Electronic Resource
    Electronic Resource
    Kinetic and thermodynamic study of the mechanism of reversible intermolecular electron-transfer reactions between horse heart cytochrome c and a series of cobalt imine complexes (1997)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 39-46 
    Details
    ISSN: 0947-6539
    Keywords: cobalt ; cytochrome c ; electron transfer ; kinetics ; volume profile ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Kinetics and Thermodynamics of the Reversible Outer-Sphere Electron-Transfer Reactions between Horse Heart Cytochrome cII/III and [Co(phen)3]3+/2+ and [Co(bpy)3]3+/2+ were studied in detail, in particular as a function of temperature and pressure. It was possible to construct a volume profile for both reactions from the pressure data. The transition state was found to be halfway between the reactant and product states on a volume basis in all studied systems. This is in agreement with the λ≠ parameter estimated from the Marcus theory. For all the systems investigated, the differences in the activation volumes are in good agreement with the reaction volumes determined from spectrophotometric and electrochemical measurements at elevated pressure, and from the difference in the partial molar volumes of the metal complexes. The activation and reaction volumes of the bipyridine system are significantly smaller than those of the corresponding phenanthroline and terpyridine systems. A detailed mechanistic analysis is presented. The results show that the different kinetic and thermodynamic techniques employed complement one another.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19970030108
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    REACTIVITY OF NUCLEOPHILES TOWARDS X-3-(p-TOLYLSULFONYL)-1,2,3-BENZOXATHIAZOLE 2,2-DIOXIDES: KINETICS, ACTIVATION VOLUMES AND MECHANISM (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 175-181 
    Details
    ISSN: 0894-3230
    Keywords: cyclic sulfamates ; nucleophiles ; reactivity ; kinetics ; mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The kinetics of the reaction of four X-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxides (X=5-Cl, 5-Br, 5-NO2 and 6-NO2) with hydroxide ion and imidazole in aqueous acetonitrile and aqueous ethanol solutions were investigated at various pressures. The volumes of activation were all found to be negative and consistent with a bimolecular reaction involving considerable solvent electrostriction. No significant dependence on the solvent composition was found. © 1997 by John Wiley & Sons, Ltd.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and Mechanism of the Outer-Sphere Oxidation of Horse-Heart Cytochrome c by an Anionic Chromium(v) Complex - Kinetic Evidence for Precursor Formation and a Late Electron-Transfer Transition State (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1805-1812 
    Details
    ISSN: 1434-1948
    Keywords: Cytochrome c ; Chromium(v) ; Saturation kinetics ; Separation of K and kET ; Volume profile ; Kinetics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The irreversible outer-sphere electron-transfer reaction between trans-bis(2-ethyl-2-hydroxybutanoato(2-))oxochromate(v) and cytochrome cII was investigated as a function of pH, concentration, temperature and pressure. The plot of the observed pseudo-first order rate constant as a function of the CrV concentration shows a clear trend towards saturation at higher CrV concentrations, from which the precursor formation constant and the electron-transfer rate constant could be separated (K = 37 ± 5 M-1 and kET = 1510 ± 180 s-1 at pH 4.8 and 279 K). In the low CrV concentration range the second-order electron-transfer rate contants were measured as a function of temperature (ΔH# = 20.9 ± 0.6 kJ mol-1; ΔS# = -79.9 ± 2.1 J K-1 mol-1; ΔG# (279 K) = 43.2 kJ mol-1). High-pressure experiments were performed at two different pH values. The kinetic (stopped-flow) and thermodynamic (electrochemical) measurements as a function of pressure enabled the construction of a volume profile for the system at 279 K. The activation volumes for the redox process are -9.2 ± 0.2 (pH 5.0) and -11.1 ± 0.8 cm3 mol-1 (pH 4.7), and the overall reaction volumes were estimated to be -7 ± 2 (pH 5.0) and -10 ± 2 cm3 mol-1 (pH 4.7) . The transition state of the redox reaction lies to a large extent on the product side and can be described as “late”. The results are discussed in comparison to earlier measurements using cobalt and ruthenium complexes as reaction partners for cytochrome c.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 4
    Electronic Resource
    Electronic Resource
    Electronically Tuned trans Labilization Controls the Substitution Behavior of RhodoximesThe authors acknowledge financial support from the Deutsche Forschungsgemeinschaft, Fonds der Chemischen Industrie, MURST, and the Max Buchner Forschungsstiftung. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 34 (1995), S. 2245-2247 
    Details
    ISSN: 0570-0833
    Keywords: kinetics ; reaction mechanisms ; rhodium compounds ; substitutions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.199522451
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    Paper (German National Licenses)
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