Effect of solvent on the reactions of coordination complexes. Part 16. Kinetics and mechanism of complexation of oxalatopentaammine-cobalt(III) with nickel(II) in methanol-water medium

Dash, Anadi C. ; Pradhan, Jyotshamayee (1992) Effect of solvent on the reactions of coordination complexes. Part 16. Kinetics and mechanism of complexation of oxalatopentaammine-cobalt(III) with nickel(II) in methanol-water medium International Journal of Chemical Kinetics, 24 (2). 155–164. ISSN 0538-8066

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/kin.550...

Related URL: http://dx.doi.org/10.1002/kin.550240204

Abstract

The kinetics of reversible complexation of oxalatopentaammine cobalt(III) with Ni2+ has been investigated in MeOH + water media (0-50 (v/v) % MeOH) at 15.0-35.0°C and I = 0.10 mol dm-3. Analysis of rate data indicates that the monobonded complex [(NH3)5 CoOCOCO2Ni]3+ in which Ni2+is bound to the end carboxylate group is the possible reaction intermediate. The formation and dissociation rates of such a species are rate limiting for the overall formation and dissociation of the binuclear species, in which Ni2+ is chelated by the oxalate moiety. The rate and activation parameters for formation and dissociation of the binuclear species are moderately solvent sensitive and solvent structural effects are discernible in the nonlinear variations of ΔH and ΔS with solvent composition. The log kr vs. Grunwald Winstein parameter (YBu±cl) plot for the dissociation of the binuclear species is markedly nonlinear.

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