INADA Yasuhiro Nagoya University, Graduate School of Science, Research Associate, 物質科学国際研究センター, 助手 (60242814)
TAKAGI Hideo Nagoya University, Graduate School of Science, Associate Professor, 大学院・理学研究科, 助教授 (70242807)
We can expect the enhancement of the selectivity and sensitivity in analysis by introducing the axis of time. We believe that a key point of the clarification of the mechanisms and reactivities of the reactions in solution is to detect and analyze the reaction intermediates and transition states. Our purpose is to develop the so-called dynamic Analytical Chemistry. We systematically pursued the mechanistic study on the reactions concerning metal ions in solution for Analytical Chemistry.
(1) The relation between the solvation structures of metal ions and their reactivities has been clarified based on the following results : (a) the solvation structures of metal ions determined by EXAFS technique, (b) the kinetics and mechanism of the solvent exchange determined by NMR technique, and (c) the transition states of the water exchange on the transition metal (II) ions evaluated by the ab initio molecular orbital method.
(2) The solvent, chelate, and pressure effects for the formation of the m
etal complexes of ligands with stereochemical character have been clarified based on the following mechanisms : (a) the mechanism for the formation and deprotonation of the sitting-atop complexes, (b) the mechanism for the metal ion incorporation of the polyol complexes of boric acid, (c) the cyclopalladation mechanism, and (d) the mechanism for complexation of beryllium (II) ion in non-aqueous solution.
(3) The outer-sphere electron transfer reactions between metal (II/III) complexes have been systematically investigated where the structural rearrangement in the inner-sphere is the rate-determining step, and the so-called gated mechanism has been clarified in detail.
(4) We pursued the methodology for dynamic analytical chemistry. Detection and analysis of the unstable reaction intermediates produced during reactions have been performed. We developed a time-resolved stopped-flow EXAFS instrument, a spectrophotometric cell and a stopped-flow apparatus for supercritical carbon dioxide, and a high-frequency resonance spectrometer. Less