Abstract
Rate constants and activation parameters for the aquation of 12 saturated amines from pentacyanoamineferrate(I1) in 1 M pyridine solutions are reported. While AG* values do not correlate with AGIO (for the ionization of the conjugate acid) or with u* and E, Taft's constants, an isokinetic relationship is found. For the series (CH3)xSH3_, and RSH2, AP correlates with A,' in water and each series shows an independent correlation of AS* with B,. These results are interpreted in terms of an adapted Caldin and Benetto's model for exchange reactions, the main contribution to the changes in activation parameters arising seemingly from the energetics of transfer of the released ligand to bulk water. This small contribution to the activation process in water is rendered observable by the remarkable insensitivity of the rate process to inner bonding effects.
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