| Project/Area Number |
60470047
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
無機・錯塩・放射化学
|
|---|
| Research Institution | HIROSHIMA UNIVERSITY |
|---|
Principal Investigator |
HAYAMI Yoneda Department of Chemistry, Faculty of Science, Hiroshima University, 理学部, 教授 (00031740)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
HIROSHI Nakazawa Department of chemistry, Faculty of Science, Hiroshima University, 理学部, 助手 (00172297)
KATSUHIKO Miyoshi Department of Chemistry, Faculty of Science, Hiroshima University, 理学部, 助手 (60033924)
YOSHIHIKO Kushi College of General Education, Osaka University, 教養部, 教授 (40033906)
|
|---|
| Project Period (FY) |
1985 – 1986
|
| Project Status |
Completed (Fiscal Year 1986)
|
| Budget Amount *help |
¥7,500,000 (Direct Cost: ¥7,500,000)
Fiscal Year 1986: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1985: ¥7,000,000 (Direct Cost: ¥7,000,000)
|
|---|
| Keywords | d-tartrate / chiral discrimination / optical resolution / diasteremeric salt / spontaneous resolution / chromatographic resolution / tetrahedral organometallic complex |
|---|
| Research Abstract |
1. The crystal structure analysis was made for three different diastereomeric salts containing <LAMBDA> - <[Co(en)_3]^(3+)> and d- <tart^(2-)> ions, and a unique face-to-face ion-pair structure was found in common in these crystals. This unique ion-pair structure ( <C_3> association) was assumed to be the origin of chiral discrimination.
2. Concerning the mechanism of chiral discrimination by <[Sb_2(d-tart)_2]^(2-)> , the L-J model proposed previously could explain the efficiency of enantiomer separation for a series of <[Co(N)_6]^(3+)> complexes. A concrete hydrogen-bonding association model was newly developed, which can similarly explain the resolution efficiency and is consistent with the CD-spectral studies.
3. Chiral metal complexes were utilized as a selector in the chromatographic resolution of metal complexes A fairly good resolution was actually attained for some neutral metal complexes and the hydrogen-bonding association could be responsible for the chiral discrimination of metal complexes in solution.
4. X-ray structural analysis made for some diastereomeric salts containing <[Sb_2(d-tart)_2]^(2-)> revealed that <[Sb_2(d-tart)_2]^(2-)> approaches <[Co(en)_3]^(3+)> or <[Co(gly)(en)_2]^(2+)> along the (pseudo) <C_3> axis to form triple hydrogen bonds to the axial NH protons. This result supports the hydrogen-bonding association model assumed in the interpretation of chromatographic resolution of <[Co(N)_6]^(3+)> -type complexes.
5. X-ray analysis was made for M[Co(edta)]・n <H_2O> with M = Li,Na,K,Rb,Cs,Mg,Ca,Sr,and Ba, to check if the crystal is spontaneously resolved or not. The results were discussed in terms of various packing modes
6. Chromatographic resolution was attempted for tetrahedral organometallic complexes with no net charge. Induced CD spectra and TLC were found useful to search for optimum conditions of optical resolution.
|
