| Project/Area Number |
09640669
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | NARUTO UNIVERSITY OF EDUCATION |
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Principal Investigator |
KITA Masakazu NARUTO UNIVERSITY OF EDUCATION,College of Education, Associate Professor, 学校教育学部, 助教授 (20177827)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Keywords | first-Ordter asymmetric transtormation / Second-Order asymmetric transformation / cobalt(III) complex / kinetics of Mutardation / activation energy / solubility / optical ailivity / N-(S-proline) dithiocarbamate / R-システイン / 反応速度 / 活性化パラメーター / S-プロリルジチオカルバマト / クロム(III)錯体 |
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| Research Abstract |
The spectrum of tris{N-(S-proline)dithiocarbamato}cobaltate(III) : [Co(S-prodtc)_3]^<3-> is similar to that of tris(dimethyldithiocarbamato)cobalt(III) so that the former complex shoud have [Co(S)_6] chromophore. The proline's carboxyl groups can not coordinate to cobalt(III) Ion. This complex shows mutarotation but the isomer ratio can be fixed by adsorption on anion exchange resin of QAE-Sephadex. Furthermore, he column chromatographic technique gave optically pure diastereomers. On the other hand, the second-order asymmetric transfomation in the barium salt produced the pure DELTA isomer. At low temperature (193K) the ^1H NMR spectrum of K_3[Co(S-prodtc)_3] in methanol solution shows that of the pure DELTA isomer. This system will be able to yield new informations on asymmetric transformation.
The mutarotation of the fac-[Co(R-cysteinato-N,S)_3]^<3-> complex in 0.1 M Li_2(R-cysteinate) aqueous solution has been reported last year on the second-order asymmetric transformation and its kinetics. Now we also confirm that isomer ratio can be frozen by adsorption on anion exchange resin. The examination of the effect of free R- or S-cysteinate ion indicates that the inversion around cobalt center competes with the replacement of free R-cysteinate ion.
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