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2003 Fiscal Year Final Research Report Summary

PRECISE SYNTHESES AND FUNCTIONALITIES OF GIANT ORGANOMETALLIC MOLECULES

Research Project

Project/Area Number 14205127
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOSAKA UNIVERSITY

Principal Investigator

TAKAHASHI Shigetoshi  OSAKA UNIVERSITY, ISIR (SANKEN), PROFESSOR, 産業科学研究所, 教授 (70029875)

Co-Investigator(Kenkyū-buntansha) TAKEI Fumie  OSAKA UNIVERSITY, ISIR (SANKEN), TECHNICAL STAFF, 産業科学研究所, 教務職員 (30252711)
ZHOU Da-yang  OSAKA UNIVERSITY, ISIR (SANKEN), RESEARCH ASSOCIATE, 産業科学研究所, 助手 (00324848)
ONITSUKA Kiyotaka  OSAKA UNIVERSITY, ISIR (SANKEN), ASSOCIATE PROFESSOR, 産業科学研究所, 助教授 (10244633)
Project Period (FY) 2002 – 2003
Keywordsorganometallic compounds / giant molecule / helix / dendrimer / polyisocyanide / precise polymerization
Research Abstract

In this research project, we have worked on the synthesis of giant organometallic molecules with definite and characteristic three-dimensional structures by utilizing structural flexibility and specific reactivities of organometallic compounds, and on the development of new molecular functionalities. Our research has been focused on dendritic and helical chiral macromolecules, and we have obtained the following results:
(1) Platinum-acetylide dendrimers having porphyrin at the core were prepared by a convergent method up to the third generation, and the intramolecular energy-transfer from platinum-acetylide moieties to the porphyrin core was observed.
(2) Efficient synthetic route for platinum-acetylide dendrimers was developed, and the sixth dendrimer that is the largest organometallic dendrimer so far was precisely prepared by a divergent method.
(3) Ruthenium-acetylide dendrimers having bridging ligands derived from triarylamine were prepared, and the relatively large interaction among metal moieties was observed.
(4) Helical chiral polyisocyanides having ferrocenyl groups, which showed a good redox property, as pendants were precisely synthesized. The polyisocyanides showed reversible conformational change responding to an electrochemical stimulus against the ferrocenyl pendants.
(5) Intramolecular energy transfer was observed in the helical chiral polyisocyanides with porphyrin pendants. We found that the helical structure enhanced the efficiency of the energy transfer, and that the functional group binding the porphyrin pendants to the main chain of the polyisocyanides affected the efficiency of the energy transfer.
(6) One handed helical poly(aryl isocyanide)s with bulky substituents at ortho-position of the aryl groups were predominantly prepared by using organorhodium complexes as initiators.

  • Research Products

    (36 results)

All Other

All Publications (36 results)

  • [Publications] K.Onitsuka, M.Yamamoto, S.Suzuki, S.Takahashi: "Structure and Reactivity of (η^3-Indolylmethyl)palladium Complexes Generated by the Reaction of Organopalladium Complexes with o-Alkenylphenyl Isocyanide"Organometallics. 21巻・4号. 581-583 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 鬼塚清孝, 高橋成年: "遷移金属錯体触媒によるらせん高分子の精密合成"触媒. 44巻・5号. 334-339 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yamamoto, K.Onitsuka, M.Uno, S.Takahashi: "Synthesis of enantiopure planar-chiral cyclopentadienyl-ruthenium binuclear complexes bridged by aromatic systems"J.Chem.Soc., Dalton Trans.. 7号. 1473-1478 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 武井史恵, 鬼塚清孝, 高橋成年: "らせんキラルなナノサイズ有機分子の合成と性質"マテリアルインテグレーション. 15巻・8号. 39-43 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 鬼塚清孝, 高橋成年: "巨大有機金属分子の分子設計と精密合成"マテリアルインテグレーション. 15巻・8号. 44-47 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 周大揚, 高橋成年: "不飽和化合物から有用複素環化合物の一段合成法の開発研究"マテリアルインテグレーション. 15巻・8号. 48-50 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Onitsuka, S.Suzuki, S.Takahashi: "A novel route to 2,3-disubstituted indoles via palladium-catalyzed three-component coupling of aryl iodide, o-alkenylphenyl isocyanide and amine"Tetrahedron Lett.. 43巻・35号. 6197-6199 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 鬼塚清孝, 松嶋雄司, 高橋成年: "面不斉シクロペンタジエニル後周期遷移金属錯体の創製と反応の立体化学"有機合成化学協会誌. 60巻・8号. 752-761 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Onitsuka, H.Kitajima, M.Fujimoto, A.Iuchi, F.Takei, S.Takahashi: "Platinum-acetylide dendrimers possessing a porphyrin core"Chem.Commun.. 21号. 2576-2577 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] D.-Y.Zhou, E.Yoneda, K.Onitsuka, S.Takahashi: "Ruthenium-catalyzed carboriylation of allene : direct synthesis of methacrylates and methacrylamides"Chem.Commun.. 23号. 2868-2869 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Onitsuka, A.Shimizu, S.Takahashi: "A divergent approach to the precise synthesis of giant organometallic dendrimers using platinum-acetylides as building blocks"Chem.Commun.. 2号. 280-281 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] F.Takei, S.Nakamura, K.Onitsuka, A.Ishida, S.Tojo, T.Majima, S.Takahashi: "Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants"Chem.Lett.. 32巻・6号. 506-507 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Hida, F.Takei, K.Onitsuka, K.Shiga, S.Asaoka, T.Iyoda, S.Takahashi: "Synthesis and Property of Helical-chiral Polyisocyanides bearing Ferrocenyl Groups as Pendants"Angew.Chem.Int.Ed.. 42巻・36号. 4349-4352 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Shiga, K.Ishii, T.Miura, J.Abe, T.Yamagishi, S.Asaoka, T.Iyoda, F.Takei, K.Onitsuka, S.Takahashi: "Chiroptical Properties of Helical Poly(aryl isocyanide)s Bearing m-Substituted Azobenzene Moiety"Trans.Mater.Res.Soc.Jpn.. 28巻・3号. 557-560 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Onitsuka, S.Takahashi: "Metallodendrimers Composed of Organometallic Building Blocks"Top.Curr.Chem.. 228巻. 36-63 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E.Yoneda, S.-W.Zhang, D.-Y.Zhou, K.Onitsuka, S.Takahashi: "Ruthenium-Catalyzed Cyclocarbonylation of Allenyl Alcohols and Amines : Selective Synthesis of Lactones and Lactams"J.Org.Chem.. 68巻・22号. 8571-8576 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] D.-Y.Zhou, S.-W.Zhang, K.Oniisuka, S.Takahashi: "Rhodium-Catalyzed Carbonylation of Norbornene under Water-Gas-Shift Reaction Conditions. Selective Formation of Co-dimeres with Lactone Terminus"Chem.Lett.. 33巻・1号. 70-71 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Matsushima, K.Onitsuka, S.Takahashi: "Stereoselective ligand-exchange reaction of planar-chiral cyclopentadienyl-ruthenium complexes : thermodynamic control of configuration at a stereogenic metal center"Dalton Trans.. 4号. 547-553 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Onitsuka, M.Yamamoto, S.Suzuki, S.Takahashi: "Structure and Reactivity of (η^3-Indolylmethyl)palladium Complexes Generated by the Reaction of Organopalladium Complexes with ο-Alkenylphenyl Isocyanide"Organometallics. 21. 581-583 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, S.Takahashi: "Precise synthesis of helical chiral polymers catalyzed by transition metal complexes"Syokubai. 44. 334-339 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Yamamoto, K.Onitsuka, M.Uno, S.Takahashi: "Synthesis of enantiopure planar-chiral cyclopentadienyhl ruthenium binuclear complexes bridged by aromatic systems"J. Chem. Soc., Dalton Trans.. 1473-1478 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Takei, K.Onitsuka, S.Takahashi: "Synthesis and property of nano-sized helical chiral polymers"Materials Integration. 15. 39-43 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, S.Takahashi: "Molecular design and precise synthesis of macromolecular organometallic complexes"Materials Integration. 15. 44-47 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D.-Y.Zhou, S.Takahashi: "Direct synthesis of heterocyclic compounds from unsaturated substrates"Materials Integration. 15. 48-50 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, S.Suzuki, S.Takahashi: "A novel route to 2,3-disubstituted indoles via palladium-catalyzed three-component coupling of aryl iodide, ο-alkenylphenyl isocyanide and amine"Tetrahedron Lett.. 43. 6197-6199 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, Y.Matsushima, S.Takahashi: "Synthesis and stereochemistry of planar-chiral cyclopentadienyl complexes of late transition metals"Yuki Gosei Kagaku Kyokaishi. 60. 752-761 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, H.Kitajima, M.Fujimoto, A.luchi, F.Takei, S.Takahashi: "Platinum-acetylide dendrimers possessing a porphyrin core"Chem. Commun.. 2576-2577 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D.-Y.Zhou, E.Yoneda, K.Onitsuka, S.Takahashi: "Ruthenium-catalyzed carbonylation of allene : direct synthesis of methacrylates and methacrylamides"Chem. Commun.. 2868-2869 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, A.Shimizu, S.Takahashi: "A divergent approach to the precise synthesis of giant organometallic dendrimers using platinum-acetylides as building blocks"Chem. Commun.. 280-281 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Takei, S.Nakamura, K.Onitsuka, A.Ishida, S.Tojo, T.Majima, S.Takahashi: "Preparation and Photochemical Properties of Polyisocyanides with Regularly. Arranged. Porphyrin Pendants"Chem. Lett.. 32. 506-507 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Hida, F.Takei, K.Onitsuka, K.Shiga, S.Asaoka, T.Iyoda, S.Takahashi: "Synthesis and Property of Helical-chiral Polyisocyanides bearing Ferrocenyl Groups as Pendants"Angew. Chem. Int. Ed.. 42. 4349-4352 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Shiga, K.Ishii, T.Miura, J.Abe, T.Yamagishi, S.Asaoka, T.Iyoda, F.Takei, K.Onitsuka, S.Takahashi: "Chiroptical Properties of Helical Poly(aryl isocyanide)s Bearing m-Substituted Azobenzene Moiety"Trans. Mater. Res. Soc. Jpn.. 28. 557-560 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Onitsuka, S.Takahashi: "Metallodendrimers Composed of Organometallic Building Blocks"Top. Curr. Chem.. 228. 36-63 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E.Yoneda, S.-W.Zhang, D.-Y.Zhou, K.Onitsuka, S.Takahashi: "Ruthenium-Catalyzed Cyclocarbonylation of Allenyl Alcohols and Amines: Selective Synthesis of Lactones and Lactams"J. Org. Chem.. 68. 8571-8576 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] D.-Y.Zhou, S.-W.Zhang, K.Onitsuka, S.Takahashi: "Rhodium-Catalyzed Carbonylation of Norbornene under Water-Gas-Shift Reaction Conditions. Selective Formation of Co-dimeres with Lactone Terminus"Chem. Lett.. 33. 70-71 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Matsushima, K.Onitsuka, S.Takahashi: "Stereoselective ligand-exchange reaction of planar-chiral cyclopentadienyl-ruthenium complexes : thermodynamic control of configuration at a stereogenic metal center"Dalton Trans.. 547-553 (2004)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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