Thermodynamic and Mechanistic Studies on Reactions of Metal Complexes in Solution

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The purpose of this research is to study reactions of metal complexes in solution by thermodynamic and kinetic approaches.(1) Characterization of metal complexes in solution: On the basis of stability constants and reaction heats of complexation for phDTA as a ligand, energetic relations for complexation were clarified. Possible structures of the phDTA complexes in solution were discussed.(2) Studies on mechanisms of metal complex formation: Activation volumes for rapid complex formation in various solvents were obtained by using the high-pressure stopped-flow technique. The reaction mechanism has been related with the bulkiness of solvents and ligands.(3) Studies on mechanisms of solvent exchange on metal(II) ions: On the basis of activation volumes for solvent exchange determined by using high-pressure multinuclear NMR, discussions have been made on the relation between mechanisms and the solvent bulkiness.The special feature of the present research is to consider thermodynamic and kinetic behaviors of metal complexes in solution on the basis of reaction volumes and activation volumes. For this purpose we developed a high-pressure stopped-flow apparatus, high-pressure multinuclear NMR probes, a high-pressure ultrasonic absorption cell, automatization of a system for calorimetry and high precision dilatometers. All these have gained international recognition.