Summary
The solvolysis of the title complex is slower in 0 to 70% v/v aqueous dioxan than in aqueous acetonitrile at 40, 45, 50 and 55° C, a fact that is attributed to the higher basicity and ionizing power of the latter solvent mixtures. The observed non-linearity for logk (solvolysis) versus 1/D plots was interpreted in terms of the relative stability of ground and transition state species. The calculated Gibbs free energy for transfer of the species in the transition state is consistent with the extreme stretching of the chlorinecobalt bond, a result which confirms the interchange dissociative mechanismI d for the complex under study.
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Sidahmed, I.M., Ismail, A.M. The solvolysis oftrans-[Co(4-Mepy)4Cl2]ClO4 in water: acetonitrile and water: dioxan mixtures. Transition Met Chem 12, 29–33 (1987). https://doi.org/10.1007/BF01023125
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DOI: https://doi.org/10.1007/BF01023125