1988 Fiscal Year Final Research Report Summary
Chiral Discrimination of Metal Complexes by Their Solubility Phase Diagrams
| Project/Area Number |
60430013
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | Osaka University |
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Principal Investigator |
KOMORITA Takashi Assistant professor Department of Chemistry, Faculty of Science, Osaka University, 理学部, 講師 (90028209)
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| Co-Investigator(Kenkyū-buntansha) |
FUYUHIRO Akira Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (90156951)
YAMANARI Kazuaki Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (40116124)
MATSUOKA Nobuko Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (30028203)
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| Project Period (FY) |
1985 – 1988
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| Keywords | Metal complex / Solubility phase diagram / Chiral discrimination / Spontaneous resolution / Diastereomer / Optical resolution / Heteropoly acid / シクロデキストリン |
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| Research Abstract |
The binary and ternary solubility phase diagrams for the following systems were determined; [Co(leu)(NH_3)_4]Br_2, [CoCO_3(en)_2]Br, (NH_4)_6[Co_2Mo_<10>O_<38>H_4].7H_2O,[Co(diNOsar)]X_3, [Co(Me_2dtc)(en)_2]X_2, and [Co(ox)(en)_2](meso-tart)_<1/2>. Spontaneous resolution was found for [CoCO_3(en)_2]Br and for (NH_4)_6[Co_2Mo_<10>O_<38>H_4 ・7H_2O. The former complex crystallizes sa both a racemic compound (below 15 ゜C) and conglomerate (above 15 ゜C). The latter one is the first heteropoly acid forming a conglomerate. In the ternary phase diagrams of Co(leu)(NH_3)_4 Br_2, the only one isotherm was found and the composition of the solid phase changed according to the solution composition. This means the existence of solid solution, which was supported by the smae IR spectra and X-ray powder patterns of [Co(L-leu)(NH_3)_4]Br_2 and [Co(DL-leu)(NH_3)_4]Br_2. This is very important to clarify the nature of chiral discrimination. Some metal complexes were kinetically resolved by drystallization in the presence of chiral additives. This resolution mechanism is best explained in terms of streoselective adsorption of the chiral additives at the crystal surfaces of one enantiomer with the same absolute configuration as that of the chiral additives. The chromatographic column prepared from SP-Sephadex C-25 resins and -and -( -cyclodextrinato)bis(ethylenediamine)cobalt(III)(1+) chloride could be successfully applied to the optical resolution of anionic complexes containing amino acids.
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