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1990 Fiscal Year Final Research Report Summary

Exploitation of Superstructure Porphyrin and Other Functional Complexes : Structure-Function Relationship.

Research Project

Project/Area Number 01470046
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionThe University of Tokyo

Principal Investigator

MIYAMOTO Takeshi  Faculty of Science, The University of Tokyo, Associate Professor, 理学部・化学科, 助教授 (30011604)

Co-Investigator(Kenkyū-buntansha) ICHIDA Hikaru  Faculty of Science, The University of Tokyo, Research Associate, 理学部化学科, 助手 (10176290)
Project Period (FY) 1989 – 1990
KeywordsSuperstructure / Porphyrin / Complexes / Structure-Function / Platinum
Research Abstract

1. Syntheses of Superstructure Porphyrin and Oxygenation Reaction.
A new bulky porphyrin, meso-tetrakis (2-methoxy-5, 5, 8, 8-tetramethyl-6, 6, 7, 7-tetrahydro-1-anthryl) porphyrin (abbr. AP) was synthesized. Four atropisomers (alphabetaalphabeta, alphaalphabetabeta, alphaalphaalphabeta, alphaalphaalpha) were separated and purified by column chromatography. The isomers all showed remarkable high thermal stability toward atropisomerization. Under a high temperature (ca. 190^OC) in 2- (2-methoxyethoxy) ethanol, ruthenium (II) ion was incorporated into each isomer with the retention of the ligand conformation. The stereoselectivity of the isomeric ruthenium (II) porphyrins to incoming ligands (py or CO) was examined by ^1H-NMR spectroscopy.
Another ruthenium porphyrin, tetrakis (2,6-difluorophenyl) porphinato ruthenium (II) (CO) (N-Melm), was prepared. It catalyzed oxidation of hydrocarbons (styrene, alpha-methylstyrene, cyclooctene or cyclohexane) by use of t-BuOOH or hypochlorite as oxidant.
2. Syntheses and Structure of Antineoplastic Platinum Complexes.
A 1R, 2R-diaminocyclohexaneplatinum (II) complex of B_2O_5H_2^<2->, (C_6H_<14>N_2)Pt(B_2O_5H_2)・H_2O, is synthesized by reacting (C_6H_<14>N_2)Pt(OH)_2 with boric acid in the presence of dipotassium tetraborate tetrahydrate in aqueous solution. X-ray structural analysis revealed that the B_2O_5H_2^<2-> anion and the platinum (II) cation from a six-membered chelate.
A series of new dinuclear platinum (II) complexes, [PtL_2(slac)]_2・H_2O where slac = sulfoacetate dianion ; L_2 = 1,2-diaminocyclohexane (1a-1c) or 1,2-diaminoethane (2), L = isopropylamine (3) or ammine (4), have been prepared from the reaction of [PtL_2(OH)_2] with sulfoacetic acid. They have di-mu-carboxylato bridged dinuclear zwitterionic structures in crystals. Among them, complexes (1a-1c) show significant antitumor activities against mice leukemia L1210.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 高木 繁、宮本 健、浜口 美保、佐佐木 行美、松村 竹子: "Synthesis and Characterization of Tetrakis(2,6ーdifluorophenyl)porphinato Ruthenium(II)(CO)(NーMelm)" Inorg.Chim.Acta. 173. 215-221 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 雨谷 敬史、宮本 健、市田 光、佐佐木 行美: "Preparation and Crystal Structure of a New Gold(I)ComPlexes Linked to Pyrimidines." Bull.Chem.Soc.Jpn.62. 1078-1080 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 宮本 健、奥出 幸二郎、前田 和之、市田 光、佐佐木 行美、田代田 鶴子: "Synthses,Spectroscopic Properies,Crystal Structures,and Antitumor Activities of Optically Isomeric Mandelate Chelates,Mandelato(transー1,2diaminocyclohexane)Platinum." Bull.Chem.Soc.Jpn.62. 3239-3246 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 奥出 幸二郎、市田 光、宮本 健、佐佐木 行美: "Absolute Structure of diーμーsulfoacetatoー bis{[1R,2R)ー1,2ーdiaminocyclohexane]platinum(II)}Trihydrate." Acta Cryst.C. 45. 949-950 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 宮本 健、市田 光: "Chelate Ring Structure of a Platinum Borate" Chem.Lett.,. (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 宮本 健、市田 光: "Syntheses,Crystal Structures,and antitumor ACtivioties of Dinuclear Platinum(II)Complexes,Diーμーsulfoacetatobis[(diammine)platinum(II)]trihydrate" Bull.Chem.Soc.Jpn.(1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Takagi, T. K. Miyamoto, M. Hamaguchi, Y. Sasaki, and T. Matumura,: "Synthesis and Characterization of Tetrakis (2, 6-difluorophenyl) - porphinato Ruthenium (II) (CO) (N-Melm) ; Oxidation Reaction of Hydrocarbon Catalyzed by the Ruthenium Porphirin," Inorg. Chim. Acta,. 173,. 215-221 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Amagai, T. K. Miyamoto, H. Ichida, and Y. Sasaki,: "Preparation and Crystal Structure of New Gold (I) Complexes Linked to Pyrimidines," Bull. Chem. Soc. Jpn.62,. 1078-1080 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. K. Miyamoto, K. Okude, K. Maeda, H. Ichida, Y. Sasaki, and T. Tashiro,: "Syntheses, Crystal Structures, and Antitumor Activities of the Optically Isomeric Mandelato (trans-1, 2-diaminocyclohexane) platinum (II)," Chem. Lett.1387-1390. (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. K. Miyamoto, K. Okude, K. Maeda, H. Ichida, Y. Sasaki, and T. Tashiro,: "Syntheses, Spectroscopic Properties, Crystal Structures, and Antitumor Activities of the Optically Isomeric Mandelate Chelates, Mandelato (trons-1, 2- diaminocyclohexane) platinum (II)." Bull. Chem. Soc. Jpn.62,. 3239-3246 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. K. Miyamoto and H. Ichida,: "Chelate Ring Structure of a Platinum Borate," Chem. Lett.,.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. K. Miyamoto and H. Ichida,: "Systheses, Crystal Structures, and Antitumor Activities of Dinuclear Platinum (II) Complexes, Di-mu-sulfoacetato-bis [(diamine)platinum(II)] trihydrate." Bull. Chem. Soc. Jpn.

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

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Published: 1993-08-12  

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