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Aquation of α-cis-chloroaquoethylenediamine-N, N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study

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Summary

The displacement of chloride ligands from α-cis-chloro-aquoethylenediamine-N,N′-diacetatocobalt(III) in nonacidic aqueous solutions was followed conductimetrically at 30–45° and the products of aquation were characterised by conductance, spectral and ion-exchange techniques. The rate constants for aquation in aqueous media and in 1 : 4 v : v mixed solvents at 25° are: 4.0 × 10−5 s−1 in H2O, 2.71 × 10−5 s−1 in MeOH : H2O, 2.74 × 10−5 s−1 in EtOH: H2,O and 2.58 × 10−5 s−1 n in Me2CO : H2O. The corresponding ΔH* and ΔS* values have also been evaluated. Solvent polarity has a marked influence on the rate of chloride ion release. The aquation rate constants and the activation parameters have been correlated with solvent parameters,e.g. D, Y-values, Dimroth's ET and Kosower's Z-values and, based on these correlations, a dissociative interchange (Id) mechanism is proposed rather than dissociative as observed for some other cobalt(III) complexes.

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Chatterjee, C., Basak, A.K. Aquation of α-cis-chloroaquoethylenediamine-N, N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study. Transition Met Chem 5, 212–214 (1980). https://doi.org/10.1007/BF01396916

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