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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of substitution of cis-diaqua-bis[2-(m-tolylazo)pyridine]-ruthenium(II) ion with pyridine-2-aldoxime in EtOH-H2O mixtures (1994)
    Springer
    Transition metal chemistry 19 (1994), S. 201-204 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Kinetic and mechanistic studies on the anation of cis-[Ru(tap)2(H2O)2]2+ (where tap = 2-(m-tolylazo)pyridine) by pyridine-2-aldoxime (LH) have been made spectrophotometrically at different temperatures (35–50° C) in aqueous medium and various EtOH-H2O mixtures. The following rate law has been established at pH 5.6: k obs = k 1 k 2[LH]/(k −1 + k 2[LH]) where k 1 is the H2O dissociation rate constant of the substrate complex and k -1 and k 2 are the aquation and ligand capturing rate constants of the pentacoordinate intermediate, [Ru(tap)2(H2O)]2+. The rate constants are independent of ionic strength. The reaction rate increases with increasing pH. Activation parameters (ΔH
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00161889
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the interaction of thiourea with cis-diaquaethylene-diamineplatinum(II) perchlorate in aqueous medium (2000)
    Springer
    Transition metal chemistry 25 (2000), S. 279-282 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the interaction of thiourea with [Pt(en)(H2O)2]2+ have been studied spectrophotometrically as a function of [Pt(en)(H2O)2]2+, [thiourea] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the thiourea ligand as a neutral molecule. The reaction proceeds via a rapid outer sphere association followed by two slow consecutive steps, the second step exhibiting first order dependence on the aqua ion and thiourea concentrations. The activation parameters for both the steps have been evaluated: (ΔH 1
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007055109189
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the interaction of DL-methionine with cis-diaquaethylenediamine platinum(II) perchlorate in aqueous medium (1999)
    Springer
    Transition metal chemistry 24 (1999), S. 59-63 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the interaction of DL-methionine with [Pt(en)(H2O)2]2+ have been studied spectrophotometrically as a function of [Pt(en)(H2O)22+], [DL-methionine], PH and temperature. The reaction proceeds via a rapid outer sphere association followed by two slow consecutive steps having first order dependence on the aqua ion and methionine concentrations. Activation parameters have been evaluated using the Eyring equation. The low ΔH1
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006993423954
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of anation of hexaaquochromium(III) by 2-aminopyridine (1993)
    Springer
    Transition metal chemistry 18 (1993), S. 353-355 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The kinetics of substitution of aqua ligands from the hexaaquochromium(III) ion by 2-aminopyridine (2-ampyH+) in aqueous medium has been studied spectrophotometrically in the 40–55° C range. The rate law involving the outer sphere complex formation has been established at pH 2.7 as $$\begin{gathered} d[Cr(2 - ampy)_2 (H_2 O)_4^{3 + } ]/dt \hfill \\ {\text{ }} = \frac{{k_a K_{osc} [Cr(H_2 O)_6^{3 + } ]_{tot} [2 - ampyH^ + ]}}{{1 + K_{osc} [2 - ampyH^ + ]}} \hfill \\ \end{gathered} $$ where K osc is the outer sphere complex equilibrium constant and k a is the rate constant for conversion of the outer sphere complex to the inner sphere complex. The reaction rate is pH dependent in the range 2.0–5.0. Activation parameters have been calculated and compared with water exchange and the substitution of the hexaaquochromium(III) ion. A mechanism involving outer sphere association between the two reactant species followed by transformation of this outer sphere complex into the product by associative path (Ia) is suggested. The mechanism is supported by the activation parameters for the reaction in 20% H2O-EtOH medium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00208170
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