| Project/Area Number |
26410058
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Sophia University |
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Principal Investigator |
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| Research Collaborator |
ASADA Takumi 上智大学, 大学院理工学研究科
KURITA Rikako 上智大学, 大学院理工学研究科
KAWAMURA Akiko 上智大学, 大学院理工学研究科
HOSOYA Makoto 上智大学, 大学院理工学研究科
ARIGA Yuki 上智大学, 大学院理工学研究科
ONO Tomoyuki 上智大学, 大学院理工学研究科
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| Project Period (FY) |
2014-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | シクロアレン / シクロアルカン / ジルコニウム / 環状不飽和炭化水素 / チタン / クムレン / 共役エンイン / 五員環アレン / チタニウム / sp炭素 / 環上アレン / アルキルシリル基 / ピロール / 環状アレン / イオウ |
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| Outline of Final Research Achievements |
We previously reported that group 4 metallocenes react with [5]cumulenes and 1,3-enynes to form five-memered metallacyclalkynes and metallacycloallenes, respectively. These compounds contain highly-strained an sp-hybridized carbon atom. We focused on its biradical or carbenoid character. In this study we found haptotropic shift in the [5]cumulene complexes and revealed that the reactivity was governed by steric demand of the substituents. The 1,3-enyne reacted with 0.5 equiv of low-valent zirconcocene to afford a bimetallic complex with carbon-carbon bond fission. This reaction might involve carbenoid complex of the cycloallene. In addition we synthesized sulfur-containing five-membered cycloallene complexes and determined their molecular structure by X-ray analysis. We also investigated a possibility of an alternative precursor of low-valent zirconocene complex, Cp2Zr(dmpe) (dmpe = dimethylphosphinoethane), and could prepare five-membered cycloallenes from that complex.
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