| Project/Area Number |
08044046
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| Research Category |
Grant-in-Aid for international Scientific Research
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| Allocation Type | Single-year Grants |
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| Section | Joint Research |
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| Research Field |
Inorganic chemistry
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| Research Institution | Hokkaido University |
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Principal Investigator |
SASAKI Yoichi Hokkaido University, Division of Chemistry, professor, 大学院・理学研究科, 教授 (30004500)
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| Co-Investigator(Kenkyū-buntansha) |
LAMPRECHT Gert J. The University of Orange Free State, Department of Chemistry, professor, 化学科, 教授
SYKES A.G. ニューカッスル大学, 化学科, 教授
UMAKOSHI Keisuke Hokkaido University, Division of Chemistry, instructor, 大学院・理学研究科, 助手 (20213481)
ICHIMURA Akio Osaka-City University, Department of Chemstry, professor, 理学部, 教授 (50047396)
NAGASAWA Akira Saitama University, Department of Chemstry, professor, 理学部, 教授 (40108452)
SYKES A.Geoffrey The University, Newcastle-upon-Tyne, Department of Inorganic Chemistry, professo
SAYSELL Dabi ニューカッスル大学, 化学科, 博士研究員
阿部 正明 北海道大学, 大学院・理学研究科, 助手 (90260033)
今村 平 北海道大学, 大学院・理学研究科, 助教授 (90113521)
LAMPRECHT Ge オレンジ自由州立大学, 教授
MCFARLANE Wi ニューカッスル大学, 化学科, 教授
A.GEOFFREY S ニューカッスル大学, 化学科, 教授
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| Project Period (FY) |
1996 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥9,500,000 (Direct Cost: ¥9,500,000)
Fiscal Year 1997: ¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 1996: ¥5,000,000 (Direct Cost: ¥5,000,000)
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| Keywords | rhenium Complexes / redox reactions / X-ray structural analysis / oxo-bridged complexes / metal-cluster complexes / kinetic studies / carboxylate-bridged complexes / metal-metal multiple bond / オキソ錯体 / 金属間結合 / 金属間相互作用 / 複核錯体 / ロジウム錯体 |
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| Research Abstract |
The purpose of this project is to understand the correlation between the oxidation states and reactivity and that of metal-to-metal interaction and redox properties by using rhenium complexes. Rhenium is the most versatile element with respect to its variety of oxidation states, and thus its complexes are the most appropriate to study redox preperties of metal complexes. Various important complexes have been prepared at Hokkaid Universty, and their reactivities have been studied by the foreign colleagues. Also, Dr.Sayse11 of the University of Newcastle-upon-Tyne and Dr.Botha of the University of Orange-Free-State, stayd at Hokkaido University for 3 months each and contributed to significant progress of the project.
By using N,N,N,O-and N,N,O-type chelating ligands, we have isolated several mononuclear rhenium (V) complexes having incompletely chelated ligands. X-Ray structural determination of these complexes revealed complex formation steps of these chelating ligands, information which
… More
is impossible to obtain by using substitution labile metal ions. Dinuclear rhenium doubly oxo-bridged complexes have been isolated in two neighboring oxidation states, (III,IV) and (IV,IV). Their structural and redox studies show the correlation between the Re-Re bond-order and redox reactions. Study on hexanuclear rhenium sulfide clusters also revealed characteristic properties of Re-Re bond. The hexarhenium cluster, [Re_6S_8(H_2O)_6]_<2+> clusters, shows unexpectedly slow anation reactions with Cl^- or NCS^-. The remarkable inertness is difficult to understand for mononuclear rhenium (III) complexes and the effect of metal-metal bond should be taken into account. This inert nature enabled us to prepare partially substituted species of the type, [Re_6S_8(pyridine)_<6-n>Cl_n]^<(2-n)+>(n=1-3). Further studies to prepare the hexarhenium (III) complexes with pyridine derivative ligands show some redox interaction between the ligands at hexarhenium center.
We have also studied redox reactions of some dinuclear ruthenium (III) complexes with oxide and acetate bridges. Protonation at the oxide bridge remarkable change the redox potentials of the diruthenium moiety. Relevance of the proton-coupled redox reactions to some enzyme dimetal active centers have been suggested. Less
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