Effect of solvent on the reactions of coordination complexes .21. Base hydrolysis of some cis-(halogeno)(amine)bis(ethylenediamine)cobalt(III) complexes in methanol-water media: The role of substrate hydrophobicity and solvent structure

The kinetics of base hydrolysis of a series of (halogeno)(amine)cobalt(III) complexes, cis-[(en)(2)Co(B)X](2+) (B = NH3, CH3NH2, CH3CH2NH2, C6H5CH2NH2, C6H11NH2, imidazole, N-methylimidazole, benzimidazole, CH3CH(OH)CH2NH2, X = Cl, Br) have been investigated in methanol-water media (0-90 vol.% MeOH) at 15.0 less than or equal to t/degrees C less than or equal to 40.0 (0.02 mol dm(-3) NaOH). The relative second-order rate constants at ionic strength, I = 0, [(k(2)(CH))(0 s)/k(2)(0 w)], generally increased non-linearly with increasing mole fraction (X(MeOH)) of MeOH; the effect was sensitive to the bulkiness and hydrophobicity of the non-labile amine ligands. The solvent effects on rate have been interpreted in terms of the role of solvent structure and preferential solvation of the initial state and transition state, presumably due to the hydrophobic interaction. This is evident from the linear plot of log(k(2)(OH))(0 s) versus (V) over bar degrees(1/3) at 25 degrees C where (V) over bar degrees is the standard partial molar volume of the complex ion in aqueous medium at 25 degrees C. The activation enthalpies and entropies also varied non-linearly with X(MeOH) and the observed extrema in the plots of Delta H-double dagger (Delta S-double dagger) vs. X(MeOH) presumably reflected the solvent structural effect on the solvation component of these thermodynamic parameters.