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Title: Kinetic studies of substitution on [(H₂O)(tap) ₂RuORu(tap)₂(H₂O)]²⁺ ion by DL-penicillamine at physiological pH
Authors: Ghosh, Alak Kumar
Issue Date: Apr-2007
Publisher: CSIR
Abstract: The reaction of DL-penicillamine with the title complex has been studied spectrophotometrically in aqueous solution as a function of concentrations of the substrate complex and ligand, pH and temperature. The reactivity of different donor centers [i.e., (N), (N,O) and (O,O)] have been compared. At pH 7.4 the reaction is a two-step process. Unlike other systems studied with the same substrate, the second step in the present case is ligand independent, ascribed to the lower difference between the two steps (k₁ = 1.78×10⁻³ s1and k₂ = 0.67×10⁻⁴ s⁻¹ respectively at 50°C) in comparison to the other systems studied earlier (k₁~10⁻³s⁻¹ and k₂~10⁻⁵s⁻¹). An associative interchange mechanism is proposed for both the steps. The activation parameters (ΔH₁ = 19.2 ± 1 kJ mol⁻¹, ΔS₁ = -239 ± 3 JK⁻¹ mol⁻¹; ΔH₂ = 65.6 ± 5.8 kJ mol⁻¹ and ΔS₂ = 123 ± 17 JK⁻¹ mol⁻¹) support the proposition. The activation parameters have been compared with other systems studied earlier.
Page(s): 610-614
ISSN: 0376-4710
Appears in Collections:IJC-A Vol.46A(04) [April 2007]

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