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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 9, Number 1
BKCSDE 9(1)
January 20, 1988

Title	The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)2Cl2]+ in Water-t-butyl Alcohol Mixture
Author	Yu Chul Park*, Young Je Cho
Keywords
Abstract	Rates of solvolysis of trans-[Co(N-eten)2Cl2]+ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ΔV≠ obtained from pressure effect on the rate constants were 2.55∼ 5.83 cm3mol-1. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ΔH≠ and ΔS≠ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant (Ds-1). The gradient, m of Grunwald-Winstein plot for the trans-[Co(N-eten)2Cl2]+ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.
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