The kinetics of the solvolytic aquation of cis-(Bromo) (imidazole) bis(ethy1enediamine) cobalt (111) and cis-(Bromo) (N-methylimidazole) bis(ethy1enediamine) cobalt(II1) have been investigated in aqueous methanol media with methanol content 0-80% by weight and a t temperatures 40-55°C. The pseudo-first order rate constant decreases with increasing methanol content. Plots of log k$ vs. D;' (where D, is the bulk-dielectric constant of the solvent mixture) and log J Z : , ~ vs. the Grunwald-Winstein Y-solvent parameter are nonlinear, the curvature of the plots is relatively more significant for the imidazole complex. The plots of log k;, vs. molfraction of methanol (X,,,,) for both the substrates also deviate from linearity, the deviation being less and less marked, particularly for the N-methyl imidazole complex, as the temperature is increased.
Hence preferential solvation phenomenon appears to be less significant when the N-H proton of imidazole is replaced by -CH3 group. The plots of calculated values of the transfer free energy of the dissociative transition state, ci~-{[(en),Co(B)1~*}* (B = imidazole, N-methylimidazole), relative to that of the initial state, cis-[C~(en),(B)Br]~+, for the transfer of the ions from water to the mixed solvent, against X, , , , exhibit maxima at XMeOH = 0.06, 0.27, and 0.12, 0.36 and minima at XMeoH = 0.12 and 0.19 for cis-l~en~,Co~imH)Br]z~ and its N-methylimidazole analogue respectively which are in keeping with the solvent structural changes around the initial state and transition state of these substrates as the solvent composition is varied.
Plots of activation enthalpy and entropy against molfraction of the solvent mixtures exhibit maxima and minima. This type of variations of the activation parameters, AHf and AS", with XMeoH speaks of the enthalpy and entropy changes associated with the solvent-shell reorganization of the complex ions both in the initial and in the transition states which contribute appreciably to the overall activation enthalpy and entropy of the aquation reaction.