Kinetics of Formation and Dissociation of Aquocobalt(III) Complexes with Some Carboxylic Acids in Acid Perchlorate Solution

Abstract

The rates of formation and dissociation of monocarboxylic complexes of aquocobalt(III) cations with propionic, malonic, and 2-ethylmalonic acids have been measured with the stopped-flow method over a range of concentrations and temperatures in acid perchlorate media at an ionic strength 3.0 M. Although the rate constants for reactions of CoOHaq2+ with neutral ligands cover only a small range, indicating a dissociative mechanism, the associated activation parameters change cooperatively. These variations are discussed in terms of differences in the structure, proton distribution, and rates of water loss in the ion-pair precursors for the different ligands. Similar activation enthalpies of dissociation indicate a common mode of coordination, and the positive activation entropies for dissociation are consistent with a neutral leaving group.