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Thermodynamic and Mechanistic Studies on Reactions of Metal Complexes in Solution

溶液中金属配合物反应的热力学和机理研究

基本信息

批准号：
59430010
负责人：
TANAKA Motoharu
金额：
$ 23.68万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1986
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-59430010/
关键词：
Complexation reaction Reaction mechanism Heat of reaction Reaction volume Pressure effect High-pressure stopped-flow method Activation volume NMR 溶媒交換反応

项目摘要

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.

本研究的目的是从热力学和动力学的角度研究金属配合物在溶液中的反应。(1)溶液中金属配合物的表征：根据phDTA作为配体的络合稳定常数和反应热，阐明了络合的能量关系。讨论了phDTA配合物在溶液中的可能结构。(2)金属络合物形成机理的研究：采用高压停流技术得到了在不同溶剂中快速络合物形成的活化体积。反应机理与溶剂和配体的体积有关。(3)金属离子的溶剂交换机理研究：在高压多核NMR测定的溶剂交换活化体积的基础上，讨论了溶剂交换机理与溶剂体积的关系，其特点是以反应体积和活化体积为基础考虑金属配合物在溶液中的热力学和动力学行为。为此，我们开发了一种高压停流装置，高压多核NMR探针，高压超声吸收池，量热系统的自动化和高精度的温度计。所有这些都得到了国际认可。