ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 (YButCl) plot for the dissociation of the binuclear species is markedly nonlinear.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550240204
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