Summary
The kinetics of the solvolysis of thetrans-[Coen2Cl2]+ cation (en = 1,2-diaminoethane) have been investigated over a range of temperatures in water with added ethanonitrile which has much less effect on the solvent structure than the acohols already used as co-solvents with water for this solvolysis. However, the non-linear relationship obtained for the variation of log (rate constant) with the reciprocal of the dielectric constant at constant temperature shows that the effect of changing solvent structure is still important, although, as expected from the absence of pronounced extrema in the variation with composition in water + ethanonitrile of physical properties which are influenced by such changes in solvent structure, the enthalpy and entropy of activation for the solvolysis vary smoothly with composition. The application of a free energy cycle shows that changes in solvent structure affect the pentacoordinated cobalt(III) ion in the transition state more than the hexacoordinated cobalt(III) ion in the initial state.
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Groves, G.S., Wells, C.F. Kinetics of the solvolysis of thetrans-dichlorobis(1,2-diaminoethane) cobalt(III) in water + ethanonitrile mixtures. Transition Met Chem 11, 20–23 (1986). https://doi.org/10.1007/BF01064495
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DOI: https://doi.org/10.1007/BF01064495