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Hypervalency of Organogermanium Compounds-Scope and Limitation

Research Project

Project/Area Number 11640547
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKanagawa University

Principal Investigator

TAKEUCHI Yoshito  Kanagawa University, Faculty of Science, Professor, 理学部, 教授 (80012384)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1999: ¥1,900,000 (Direct Cost: ¥1,900,000)
KeywordsOrganogermanium compounds / dynamic NMR method / hyper coordination / pseudorotation / prototropy / Xray crystallographic analysis / trigonal bipyramid / high resolution solid state NMR / 固体高分解能Ge-73NMR / 有機ゲルマニウム化学 / Ge-73 NMR
Research Abstract

1 The structure of hypercoordinate organogermanium comounds in solid-ohase and in solution.
The structure of 2-(2-t-butyl-5-oxo-1, 3, 2-oxathiagermolan-2-ylthio) acetic acid (1) and its phenyl derivative (2) and their pyridiumu salts (3) and (4) was investigated. In the solid phase, all compounds investigated were in trigonal bipyramidal structure.
In solid-state, the two trigonal bipyramids are different while in solution these are equivalent in the NMR timescale. Thus, there is observed only one CH_2 proton and carbon signals, indicating a rapid exchange. Furthermore, the methylene peak split into two peaks, indicating a slow exchange. The barrier is ca 12 kcal mol^<-1>. We believe this exchange is Berry pseudorotation or turnstile rotation.
2 Hypercoordinate structure of triarylgermanes.
We prepared a variety of triarylgermanes with some ligands at ortho position such as chlorotris [2-(methoxymethyl) phenyl] germane and methyltris [2-(methoxymethyl)-phenyl] germane. Both compounds are pentavalent in a trigonal bipyramidal structure. The reason why such compounds did not show hexa or hepta coordination is not clear at all.
3 Synthesis of novel hosts modified with germanium.
We prepared a variety of novel organogermanium compounds as possible hosts for anions and neutral molecules. These include calixarenes with some side-chain containing germanium, azacrown with germanium-containing side-chain on nitrogen, and cyclophanes including germanium in the bridge.
4 High-resolution solid-state ^<73>Ge NMR spectroscopy.
We firstly observed germanium resonance of solid tetraphenylgermane in high-resolution condition. Ge-73 NMR may be a powerful tool for studying hyper valency of germanium.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Y.Takeuchi et al.: "The first observation of high-resolution solid-state ^<73>Ge NMR spectra of organogermanium compounds"J.Chem.Soc.,Chem.Commun. 687-688 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi,T.Sakurai: "The synthesis and possible transport property of a calix [4] arene modified with sidechains containing germanium"Main Group Metal Chem.. 23(5). 311-317 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi,M.Nishikawa: "Dynamic behavior of pentacoordinate organogermanium carboxylic acids and theirpyridinium salts"Heteroatom Chem. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Suzuki and Y.Takeuchi: "Synthesis of azacrown ethers modified with side-chains containing germanium"J.Organometal.Chem.. (submitted).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi, M.Nishikawa, K.Tanaka, T.Takayama, M.Imanari, K.Deguchi, T.Fujito and Y.Sugisaka: "The first observation of high-resolution solid-state ^<73>Ge NMR spectra of organogermanium compounds."Chem.Commun.. 687 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi, T.Sakurai and K.Tanaka: "The synthesis and possible transport property of a calix [4] arene modified with sidechains containing germanium."Main Group Metal Chem.. 23(5). 311 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi, M.Nishikawa, K.Tanaka, and G.Yamamoto: "Dynamic behavior of pentacoordinate organogermanium carboxylic acids and theirpyridinium salts."Heteroatom Chem.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Suzuki, T.Matsumoto, K.Tanaka, Y.Takeuchi and T.Taketomi: "Synthesis of azacrown ethers modified with side-chains containing germanium"J.Organometal.Chem.. (under submission).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Takeuchi,M.Nishikawa,etc: "First observation of high-resolution solid state Ge-73 NMR Spectra of organogermanium compounds."Chem.Commun.. 687-688 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Takeuchi,etc: "Dynamic behavior of pentacoordinate organogermanium carboxylic acids and their pyridinium salts."Heteroatom chem.. (in press).

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Takeuchi et al: "The First Observation of high-resolution solid-state 73Ge NMR Spectra"J. Chem. Soc. Chem. Communications. (in press). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Takeuchi et al.: "The Synthesis and Possible Transport Property of a calix[4]arene modified with sidechains Containing germanium"Main group Matal Chemistry. (in press). (2000)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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