Abstract
For reactions involving electron transfer or nucleophilic attack on the transition state/excited state of metal complex in aquo-organic solvent mixtures, a linear relationship between logarithms of rate constant and solvent empirical parameters can be derived. The relationship, YS = Y0 + a1X1 + a2X2 + ... + anXn, fits well for both the measured quantity in a solvent and solvent dependent property. From the quantitative estimation of the coefficients, the dominant solvent stoichiometric and other substantial medium effects on reactivities can be confirmed. Electron-transfer reaction of Co(NH3)4ox+ complex with Fe(CN)64- in six different water−cosolvent binary mixtures have been investigated (cosolvent: methanol or 1,4-dioxane 5−30% (v/v)) and the respective ket and KIP values have been experimentally determined. The ket values evaluated in mixed solvents show linearity with xorg and er-1, reflecting the individuality of the cosolvent and thereby suggesting that the relative stability of the ion pair is gov...
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