| Project/Area Number |
06044004
|
|---|
| Research Category |
Grant-in-Aid for international Scientific Research
|
| Allocation Type | Single-year Grants |
|---|
| Section | Joint Research |
|---|
| Research Institution | HOKKAIDO UNIVERSITY |
|---|
Principal Investigator |
SASAKI Yoichi Graduate School of Science, Hokkaido University, Prof., 大学院・理学研究科, 教授 (30004500)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
LEMPRECHT Ge 南アフリカオレンジ自由州立大学, 物理学科, 教授
MCFALANE William The University, Newcastle-upon-Tyne, Prof., 化学科, 教授
SYKES A.Geof 米国ニューカッスル大学, 化学科, 教授
ICHIMURA Akio Osaka City University, Faculty of Science, Asso.Prof., 理学部, 助教授 (50047396)
NAGASAWA Akira Saitama University, Faculty of Science, Prof., 理学部, 教授 (40108452)
UMAKOSHI Keisuke Graduate School of Science, Hokkaido University, Instructor, 大学院・理学研究科, 助手 (20213481)
SYKES Alfred Geoffrey The University, Newcastle-upon-Tyne, Prof.
LAMPRECHT Gert J. University of the Orange Free State, Prof.
LAMPRECHT Ge 南アフリカオレンジ自由州立大学, 物理学科, 教授
|
|---|
| Project Period (FY) |
1994 – 1995
|
| Project Status |
Completed (Fiscal Year 1995)
|
| Budget Amount *help |
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1995: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1994: ¥3,300,000 (Direct Cost: ¥3,300,000)
|
|---|
| Keywords | Redox Reactions / Clluster Complexes / Oxided Bridge / Rhenium Complexes / Ruthenium Complexes / Kinetics / Electrochemistry / Hydroxo Bridge / 金属クラスター錯体 / プロトン付加 / 電気化学 |
|---|
| Research Abstract |
This project was planned to study kinetics of redox reactions of oxobridged dinuclear complexes of heavy transition elements with special attention to the protonation at the oxide bridge associated with the redox processes. It was proposed to study with rhenium complexes, since they would take variety of oxidation states than any other elements. We have prepared number of new rhenium di (mu-oxo) complexes with different oxidation states, (III,IV) and (IV,IV), with ligands such as tris (2-pyridylmethyl) amine and its analogs, and studied their redox behavior electrochemically. Kinetic study of their redox reactions in aqueous media helped to understand the role of protonation at the oxide bridge on the reduction rate. However, the study in acetonitrile medium, which was proved to be a better solvent to study the protonation effect in electrochemical study, was suffered from some side reactions and did not provide expected information. Subsequently, we studied electrochemical and kinetic studies of proton-coupled redox reactions of related mononuclear oxorhenium (V) complexes which involve new complexes such as trans-[Re(O)(OH)(ethylenediamine)2]^<2+> and trans-[Re(O)2(imidazole)4]^+ prepared and structurally characterized in this study, and found necessary kinetic information on the redox reactions in aqueous and acetonitrile solution. In the latter solvent, proton-coupled redox behavior was studied by adding proton-donors with various pK_a values. Further kinetic study of the reduction of a ruthenium dimer, [Ru2(mu-O)(mu-CH3COO)2(bpy)2(Meim)2]^<2+>(bpy = 2,2'-bipyridine, Meim = 1-methylimidazole) gave some preliminary results on the effect of the protonation at the oxide bridge.
|
