Synthesis and Function of Organometallic Hetero-five-membered Unsaturated Molecules That Contain a Higly-strained sp-Carbon Atom
| 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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Report
(4 results)
Research Products
(22 results)
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[Journal Article] Haptotropic Shift of [5]Cumulenes in Zirconocene Complexes and Effects of Steric Factors2014
Author(s)
Noriyuki Suzuki, Takao Yoshitani, Shota Inoue, Daisuke Hashizume, Hajime Yoshida, Meguru Tezuka, Keisuke Ida, Sayoko Nagashima, Teiji Chihara, Osamu Kobayashi, Shinkoh Nanbu, Yoshiro Masuyama
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Journal Title
Organometallics
Volume: 33
Issue: 19
Pages: 5220-5230
DOI
Related Report
Peer Reviewed / Acknowledgement Compliant
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