1997 Fiscal Year Final Research Report Summary
Development of New Field of Solution Coordination Chemistry from a Viewpoint of Precursor Phenomena for "Supramolecular Effect
| Project/Area Number |
07304045
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KAIZAKI Sumio Osaka Univ.Grad.School Sci., Prof., 大学院・理学研究科, 教授 (20089874)
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| Co-Investigator(Kenkyū-buntansha) |
ISHIHARA Koji Waseda Univ., School Sci.Eng., Prof., 理工学部, 教授 (20168248)
SAWADA Kiyoshi Niigata Univ., Fac.Sci., Prof., 理学部, 教授 (40089850)
ISHIGURO Shinichi Kyusyu Univ. Fac.Sci., Prof., 理学部, 教授 (80111673)
IIDA Masayasu Nara Women's Univ.Fac.Sci., Prof., 理学部, 教授 (00107343)
FUNAHASHI Shigenobu Nagoya Univ.Grad.School Sci., Prof., 大学院・理学研究科, 教授 (30022700)
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| Project Period (FY) |
1995 – 1997
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| Keywords | Compensation Effect / Micelles / FT Raman Spectroscopy / ^2HNMR / Solution Dynmics / Solvent-Ion Cooperative Interaction / Hydrophobic Ion Association |
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| Research Abstract |
1. For redox reaction rates between dinuclear complexes [VO(sakenO)]_2(CH_2)_n(n=3,6,10,12) and Fe(III), the activation enthalpy and entropy increases with increasing n, and the complimentary effect is observed in this system.
2. The reduction potentials from oxo-bridged Ru(III) dinuclear complexes to (III,II) and (II,II) in acetonitrile are found to shift to positive (ca.1V) by addition of proton donor or BF3, and this shift and the numbers of electrons concerned are controlled by the pKa values of the proton donors.
3. The examination of the interaction of [M(en)_3]^<3+>, [M(chxn)_3]^<3+>, [M(phen)_3]^3(M=Co^<III>, Cr^<III>) with the micelles in terms of ^<59>Co NMR(Co^<III>) and ^<13>C paramagnetic relaxation (Cr^<III>) demonstrates that the extent of the interactions with sulphonic or sulfate ions and carboxylates reflects the selectivity.
4. The possibility and limitation of application for FT Raman spectroscopy to solution coordination chemistry was discussed. The dynamics of chelate ring conformation in solution state was investigated with respect to the solvent effect and temperature dependence by ^2H NMR spectra of paramagnetic Cr(III) complexes. These subjects were discussed in relation with weak interactions in the second coordination sphere.
5. The cooperative interaction between solvents and ions in highly concentrated electrolytes and hydrophobic ion association in aqueous solutions were investigated together with the complex formation in micelles. These studies will be expected to progress in connection with the mesoscopic phenomena.
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[Publications] S.Aizawa, T.Natsume, K.Hatano, and S.Funahashi: "Complexation Equilibria and Structures of Dimethyltin(IV) Complexes with N-Methyliminodiacetate, Pyridine-2,6-dicarboxylate, Ethylenediamine-N,N'-diacetate, and Ethylenediamine-N,N,N', N'-tetraacetate." Inorg.Chim.Acta. 248. 215-224 (1996)
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