| Project/Area Number |
04640581
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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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 |
TAKAHASHI Shigetoshi Osaka University, I.S.I.R., Professor, 産業科学研究所, 教授 (70029875)
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| Co-Investigator(Kenkyū-buntansha) |
UNO Mitsunari Osaka University, I.S.I.R., Research Associate, 産業科学研究所, 助手 (20213473)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1993: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1992: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Planar chirality / Cyclopentadienyl-metal / Transition metal / Optical resolution / Anion receptor / Helical chirality / Chiral recognition / Atropisomerism / シクロブタジエン / コバルト / 遷移金属錯体 / ニッケル / 面不斉 / シクロブタジエン配位子 / 金属アセチリド |
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| Research Abstract |
We have studied a new and convenient route for the syntheses of planar-chiral cyclopentadienyl-metal complexes by use of a trisubstituted cyclopentadiene having a removable chiral auxiliary.
1.Diastereomerically pure planar-chiral ferrocenes, Cp'-Rh, -Co, and-Ni complexes have been prepared by the reaction of the trisubstituted cyclopentadiene bearing a (-) -menthyl group. Removal of the (-) -menthyl group from the diastereomeric complex by the reaction with RLi or hydrolysis, which afforded the first optically pure planar-chiral Cp'-Rh, -Co, and-Ni complexes.
2.The cobalticinium complexes have been shown to behave as anion receptors which can recognize the chirality of campor-10-sulfonate.
3.Diastereomerically pure Cp'Co (tetraphenylcyclobutadiene) complexes have provided the first example which contain three different chiralities (planar, carbon-centered, and helical) in one molecule. The helical chirality found in Cp'Co (C_4Ar_4) afford a new type of atropisomerism originating from freezing bond rotation by a pile driven from Cp' ring into a four-blade windmill on the C4 ring.
The convenient synthetic route described here leads to a fairly wide range of new planar-chiral cyclopentadienyl-organometallic compounds which build up new chiral enviroments around the central metals.
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