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Design for Novel Organo Hypervalent Compounds

Research Project

Project/Area Number 11304044
Research Category

Grant-in-Aid for Scientific Research (A).

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTOHO UNIVERSITY (2000)
Hiroshima University (1999)

Principal Investigator

TAKAHASHI Masashi (2000)  Toho University, Faculty of Science, Associate Professor, 理学部, 助教授 (30171523)

秋葉 欣哉 (1999)  広島大学, 理学部, 教授 (20011538)

Co-Investigator(Kenkyū-buntansha) YAMAMOTO Yohsuke  Hiroshima University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (50158317)
AKIBA Kin-ya  Toho University, Faculty of Science, Visiting Professor, 理学部, 客員教授 (20011538)
高橋 正  東邦大学, 理学部, 助教授 (30171523)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥37,200,000 (Direct Cost: ¥37,200,000)
Fiscal Year 2000: ¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 1999: ¥29,200,000 (Direct Cost: ¥29,200,000)
Keywordshypervalent / pentacoordinate carbon species / pentacoordinate boron species / phophorane / phosphorus / arsenic / antimony / porphyrin / アンチアピコフィリシティー / 反結合性P-O軌道 / メスバウアー分光 / ハイパーバレント / S_N2反応
Research Abstract

Porphyrin complexes of group 15 : A equilibrium mixture of [(OEP)P(R)(OH)]^4Cl^-(10) and (OEP)PR(=O)(1)was obtained by the reaction of RPCl_2(R=Me, Et, Ph) and (OEP)H_2. Since the acidity of the OH group in 10 is high, 1 and 10 are selectively isolated by controlling pH for the solution of the mixture. The existence of P=O double bond in 1 is confirmed by the X-ray structural dctermination. (OEP) As (R)(=O)(14) is also obtained via [(OEP)As(R)(OH)]^<6+>X^- (13). 13 is the first arsenic porphyrin whose molecular structure is confirmed by X-ray crystallography. The acid-base equibrium between 14 and 13 is also observed. NMR indicates that the acidity of 13 is weaker than that of 10. The heterobimetallic μ-oxo porphyrins [(OEP)Al-O-E(OEP)(R)] (E=P, As) are derived by the reaction of [(OEP)Al(Me)] and the hydroxo porphyrins. The corresponding Al-Sb dinuclear porphyrin is obtained by a photo reaction. The formation of exciplex under the irradiation of light is suggested. ^<121>Sb Mossbauer … More spectra for Sb-TPP complexes indicate that the electronic state of Sb is strongly affected by the axial ligands.
Novel hypervalent pentacoordinate carbon and boron compounds : A stable pentacoordinate carbon compound [(MeO)_2C(DMA)]^+ having a 1,8-dimethoxyanthracene ((DMA)H) as a tridentate ligand is firstly isolated. The X-ray analysis definitely indicates the existence of O-C-O hypervalent bond and the density function theory (DFT) calculation also indicates the bonding interaction between C-O bond. The hypervalent pentacoordinate boron compound [(CAT)B(DMA)] (CAT=catecolate anion) is also prepared and fully specificated using an X-ray determination, ^<11>B NMR and a DFT calculation. Employing the van Koten type ligand as a flexible ligand, the second example of hypervalent carbon contpound is obtained and characterized.
anti-apicophilic phosphoranes : The anti-apicophilic spirophosphoranes having two Martin ligands (2 : O-cis) are obtained as kinetic products. 2 is highly nucleophilic compared to the apicophilic isomer (O-trans). The acidity of α-proton is high for 2, and by the reaction of its anion and benzaldehyde a hexacoordinate compound, being the intermediate species for Wittig reaction, is derived. No such a product is obtained for apicophilic isomer. Less

Report

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

    (40 results)

All Other

All Publications (40 results)

  • [Publications] Akihiro Yamamoto et al: "Phosphorus octaethyltetraphenylporphyrins [(oetpp)P(Me)(X)]PF6 (X=Me, OH, F) having saddle (X=Me) or ruffled (X=OH, F) conformations"Chem.Commun.. 147-148. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Wataru Satoh et al.: "Synthesis of unsymmetrically substituted antimony (V) tetraphenylporphyrins"Bull.Chem.Soc.Jpn.. 72. 459-463 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koichiro Toyota et al.: "A hypervalent phophorane-palladium cation complex bearing benzaldehyde"J.Chem.Res.(S). 386-387. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masaaki Nakamoto et al.: "Stable dioxaphosphirane species : Facile formation by reaction of 10_P_4 hypervalent phosphoraidewith atomosphreic oxygen"J.Am.Chem.Soc.. 121. 6958-6959. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Manabu Yasumoto et al.: "Synthesis and X-ray structure of arsenic (V) porphyrins withsymmetric diaxial ligands of Me_2 and F_2"Chem.Lett.. 791-792 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koichiro Toyata et al.: "Synthesis and crystal structure of a rhodium (III) complex bearing a hypervalent phosphorus (V) ligand as a bidentate ligand and equilibrium between bidentate and monodentate structures in solution"J.Organomet.Chem.. 586. 171-175. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kin-ya Akiba et al.: "Preparation and kinetic study of antiapicophilicity pseudorotamers of substituted spirophosphoranes with Martin ligand"Phosphorus, Sulfur Silicon. 144-146. 561-564 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kin-ya Akiba et al.: "Synthesis and isolation of stable hypervalent carbon compound (10_C_5) bearing a 1,8-dimethoxyanthracene ligand"J.Am.Chem.Soc.. 121. 10644-10645 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masaki Maeda et al.: "^<121>Sb and ^<57>Fe Mossbauer spectra of antimony-containing iron carbonyl complexes : [HSb{Fe(CO)_4}_3]^<2-> and [Sb{Sb(CO)_4}_4]^<3->"J.Radioanal.Nucl.Chem.. 239. 233-236 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Makoto Yamashita et al.: "Synthesis of a versatile tridentate anthracene ligand and its application for the synthesis of hypervalent pentacoordinate boron compounds (10-B-5)"Angew.Chem.Int.Ed.. 39. 4055-4058 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Atsushi Ishiguro et al.: "^<121>Sb, ^<57>Fe and ^<127>I Mossbauer spectroscopic study on antimony-transition metal bond in metal carbonyl derivatives of tertirary sibines"J.Organomet.Chem.. 611. 558-565 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Yamamoto,K.-y.Akiba: "The chemistry of group 15 element porphyrins bearing element-carbon bonds : synthesis and properties"J.Organomet.Chem.. 611. 200-209 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.-y.Akiba: "Chemistry of Hypervalent Compounds"Wiley-VCH. 414 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akihiro Yamamoto et al: "Phosphorus octaethyltetraphenylporphyrins [(oetpp) P(Me)(X)]PF_6 (X=Me, OH, F) having saddle (X=Me) or ruffled (X=OH, F) conformations"Chem.Commun.. 147-148 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Wataru Satoh et al: "Synthesis of unsymmetrically substituted antimony (V) tetraphenylporphyrins"Bull.Chem.Soc.Jpn.. 72. 459-463 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koichiro Toyota et al: "A hypervalent phophorane-palladium cation complex bearing benzaldehyde"J.Chem.Res.(S). 386-387 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masaaki Nakamoto et al: "Stable dioxaphosphirane species : Facile formation by reaction of 10-P-4 hypervalent phosphoraidewith atomosphreic oxygen"J.Am.Chem.Soc.. 121. 6958-6959 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Manubu Yasumoto et al: "Synthesis and X-ray structure of arsenic (V) porphyrins withsymmetric diaxial ligands of Me_2 and F_2"Chem.Lett.. 791-792 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koichiro Toyata et al.: "Synthesis and crystal structure of a rhodium (III) complex bearing a hypervalent phosphorus (V) ligand as a bidentate ligand and equilibrium between bidentate and monodentate structures in solution"J.Organomet.Chem.. 586. 171-175 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kin-ya Akiba et al.: "Preparation and kinetic study of antiapicophilicity pseudorotamers of substituted spirophosphoranes with Martin ligand"Phosphorus, Sulfur Silicon. 144-146. 561-564 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kin-ya Akiba et al.: "Synthesis and isolation of stable hypervalent carbon compound (10-C-5) bearing a 1,8-dimethoxyanthracene ligand"J.Am.Chem.Soc.. 121. 10644-10645 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masaki Maeda et al.: "^<121>Sb and ^<57>Fe Mossbauer spectra of antimony-containing iron carbonyl complexes : [HSb{Fe(CO)_4}_3]^<2-> and [Sb{Sb(CO)_4}_4]^<3->"J.Radioanal.Nucl.Chem.. 239. 233-236 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Makoto Yamashita et al.: "Synthesis of a versatile tridentate anthracene ligand and its application for the synthesis of hypervalent pentacoordinate boron compounds (10-B-5)"Angew.Chem.Int.Ed.. 39. 4055-4058 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yohsuke Yamamoto, Kin-ya Akiba: "The chemistry of group 15 element prophyrins bearing element-carbon bonds : synthesis and properties"J.Organomet.Chem.. 611. 200-209 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Atsushi Ishiguro et al: "^<121>Sb, ^<57>Fe and ^<127>I Mossbauer spectroscopic study on antimony-transition metal bond in metal carbonyl derivatives of tertirary sibines"J.Organomet.Chem.. 611. 558-565 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kin-ya Akiba, Wiley-VCH: "Chemistry of Hypervalent Compounds"414 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Yamashita,Y.Yamamoto,K.-y.Akiba,S.Nagase: "Synthesis of a versatile tridentate anthracene ligand and its application for the synthesis of hypervalent pentacoordinate boron compounds (10-B-5)"Angew.Chem.Int.Ed.. 39. 4055-4058 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Yamamoto,K.-y.Akiba: "The chemistry of group 15 element porphyrins bearing element-carbon bonds : synthesis and properties"J.Organomet.Chem.. 611. 200-209 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Toyota,Y.Yamamoto,K.-y.Akiba: "Synthesis and structures of hypervalent antimony compounds bearing antimony-group 6 transition metal bond"Organometallics. 19. 5134-5142 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Wakisaka,Y.Yamamoto,K.-y.Akiba: "Synthesis and X-ray crystal structures of hypervalent hexacoordinate antimony compounds without halogen ligands"Heteroatom.Chem.. 12. 33-37 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Ishiguro,M.Takahashi,M.Takeda: "^<121>Sb,^<57>Fe and ^<127>I Mossbauer spectroscopic study on antimony-transition metal bond in metal carbonyl derivatives of tertiary stibines"J.Organomet.Chem.. 611. 558-565 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Ikeue,Y.Ohgo,M.Nakamura,M.Takahashi,M.Takeda et al.: "Formation of pure intermediate spin complexes in highly nonplanar iron (III) porphyrins"Chem.Commun.. 1989-1990 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Nakamoto et al.: "Stable Dioxaphosphirane Species. Facile Forination by Reaction of 10-P-4 Hypervalent Phosohoranide with Atmoseheric Oxygeu"J.Am,.Chem.Soc.. 121. 6958-6959 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Akiba et al.: "Synthesis and Isolation of Stable Hypervalent Carbon Compound (10-C-5) Bearing a 1,8-Dimetaexyanthraczne Ligand"J.Am,.Chem.Soc.. 121. 10644-10645 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Mimoura et al.: "Synthesis and Charaeterization of a Hypenalent Tellurium Caticn,PheTo^<14>: A Stable Niorclassical Orium Conpocend"J.Am,.Chem.Soc.. 121. 10852-10853 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Yamamoto et al.: "Phosphorus OctaethyltetraplenylporphyrinS [(oetpp)P(Me)(X)]PF_6(X_2H_2,OH,F) Having Saddle (X=Me) N Ruffled(X=OH,F) Conforinations"J,C,S.Chem.Commun.. 147-148 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] W.Satoh.et al.: "Synthesis of un symmetrecslly Subst*tuted Antimony Torspheuylprphyrins"Bull.Chem.Soc.Jpn.. 72. 459-463 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Toyota et al.: "Syiothesis and Crystal Structure of a Rhodium(III)Complex Bearing a Hypenvalent Phosperus(IV)Ligand es a Bide*tale Ligand and Ezuili in :** be-ween Oide*mle and Hcncct*de Struifures ** Soloti*n"J.Organomental.Chem.. 586. 171-175 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K,-y,Akiba: "Chemistry of Hyperval Compounds,Chapter 1"wiley-VCH. 8 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K,-y,Akiba: "Chemistry of Hyperval Compounds,Chapter 2"wiley-VCH. 39 (1999)

    • Related Report
      1999 Annual Research Report

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

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