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Synthesis and Photoracemization of Ruthenium Complexes with Six-membered Chelate Rings

Research Project

Project/Area Number 61470048
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 InstitutionRikkyo University

Principal Investigator

MIZUMACHI Kunihiko  Rikkyo University Professor, 理学部, 教授 (00062513)

Co-Investigator(Kenkyū-buntansha) TACHIYASHIKI Satoru  Kagawa Nutrition College Assistant, 助手 (00076192)
ISHIMORI Tatsujiro  Rikkyo University Professor, 理学部, 教授 (40062492)
永井 峻  日本医科大学, 化学教室, 助手
Project Period (FY) 1986 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥5,200,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1986: ¥3,200,000 (Direct Cost: ¥3,200,000)
Keywordsruthenium complex / dipyridylamine complex / dipyridylketone complex / dipyridylmethane complex / optical resolution / ジピリジルメタン錯体 / ジピリジルアミン錯体 / ジピルジルメタン錯体 / 円偏光二色性スペクトル / 錯体の光学分割 / ジピリジルケトンールテニウム錯体 / ジピリジルアミンールテニウム錯体 / ジピリジルメタンールテニウム錯体 / ジピリジルアミン-ルテニウム錯体 / ジピリジルケトン-ルテニウム錯体
Research Abstract

1.Synthesis of complexes
The synthesis of a series of complexes with a formula of [Ru(bpy)<@D2n@>D2(L)<@D23-n@>D2]X<@D22@>D2 has been developed {L = di-2-pyridylamine (HDPA), di-2-pyridylketone (dpk), or di-2-pyridylmethane (dpm);n = 0-2}. The following new complexes were synthesized. [Ru(bpy)<@D2n@>D2(Hdpa)<@D3-n@>D2]X<@D22@>D2 (n = 0-2, X = PF<@D26@>D2, C10<@D24@>D2, CF<@D23@>D2SO<@D23@>D), ッ[Ru(bpy)<@D22@>D2(dpk)](C10<@D24@>D2)<@D22@>D2・h<@D22@>D2O, [Ru(bpy)<@D22@>D2(dpm)](PF<@D26@>D2)<@D22@>D2・H<@D22@>D2O.The following complexes were also newly obtained. [RuC1<@D22@>D2(dpk)<@D@>D2]Cl, [Ru(dpkOH)<@d22@>d2]Cl.
2. Optical resolution
The following coplexes were resolved through SP-Sephadex cation exchange chromatography or precipitation of diastereomers. Dibenzoyltartrate was effective resolving agent. [Ru(bpy)_n(Hdpa)_<3-n>]^<2+> ( n = 0-2), [Ru(bpy)_2(dpm)]^<2+>, [Ru(bpy)_2(dipyridylemthanoe)]^<2+>.
3. Photoracemization
The quantum yield of photoracemization were measured for act-[Ru(Hdpa)_3]^<2+> and act-[Ru(bpy)_2(Hdpa)]^<2+>. Themperature dependencyof quantum yield was quite similar to the case of [Ru(bpy)_3]^<2+>. The racemization may probably occur from the exited ^3Lf state.
4. Future project
Since the synthesis and the optical resolution have been well established the next step of the present work will be the determination of the quantum yields of photoracemization, and the life-time of emission of the series of the complexes at varying temperture.

Report

(4 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • 1986 Annual Research Report
  • Research Products

    (33 results)

All Other

All Publications (33 results)

  • [Publications] 三木: Bull.Chem.Soc.Jpn.59. 3275-3276 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 立屋敷: Inorg.Chem.25. 3209-3211 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 鎌田: Bull.Chem.Soc.Jpn.60. 1343-1347 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 立屋敷: Proc,XXV,Int,Cont,Coord,Chem,.314 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 立屋敷: Chem.Lett.1001-1004 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 立屋敷: Proc.xxvi.Int.Cont.Coord.Chem.B42 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 鎌田: Bull.Chem.Soc.Jpn.61. 594-596 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 鎌田: Chem.Lett.159-162 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 福地: Bull.Chem.Soc.Jpn.(1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 伊藤: Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] E. Miki: "Reactions of [Co(4-methyl-8-quinolinolato)_2(NO)(py)]with Nitrogen Oxide" Bull. Chem. Soc. Jpn.59. 3275-3276 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S. Tachiyashiki: "Hydrophobic and Steric Effects on the Ion-pair Formation of [Fe(phen)_3]^<2+> and Arenesulfonate Ions" Inorg. Chem.25. 3209-3211 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Y. Kamada: "Crystal and Molecular Structures of Two Isomers for [RuCl(qn)_2(NO)] (Hqn = 2-methyl-8-quinolinol)" Bull. Chem. Soc. Jpn.60. 1343-1347 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S. Tachiyashiki: "Photoracemization and Photosubstitution of [Ru(phen)_3]^<2+>" Proc. XXV. Int. Conf. Coord. Chem.314 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S. Tadhiyashiki: "An Acid Dependence of the Photosubstitution of Tris(1,10-phenantroline)ruthenium(II)" Chem. Lett.1001-1004 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S. Tachiyashiki: "Photosubstitution and Photoracemization of Tris(2,2'-bipyridine)ruthenium(II) in Aqueous Acidic Solutions" Proc. XXVI. Int. Conf. Coord. Chem.42 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] H. Kamada: "Photoinduced Preparation of Geometrical Isomers of [RuX(2-methyl-8-quinolinolato)_2NO] (X = Cl, Br)" Chem. Lett.159-162 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] H. Kamada: "Synthesis and Structure of cis-(O,O), trans-(N,N)- chlorobis(8-quinolinolato)nitrosylruthenium" Bull. Chem. Soc. Jpn.61. 594-596 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] T. Fukuchi: "Optical Resolution of Di-2-pyridylamine Complexes of Ruthenium(II)" Bull. Chem. Soc. Jpn.62. (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] M. Itoh: "The Two-dimentional NMR Spectra of [Ru(bpy)_2(di-2-pyridylketone)](ClO_4)_2" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 立屋敷、長尾、水町: Chem.Letts.1988年号. 1001-1004 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 福地、長尾、三木、水町、石森: Bull.Chem.Soc.Jpn.62. (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] 伊藤,水町: Bull.Chem.Soc.Jpn.

    • Related Report
      1988 Annual Research Report
  • [Publications] 荻野、水町、石森、桜井: Bull.Chem.Soc.Jpn.

    • Related Report
      1988 Annual Research Report
  • [Publications] 鎌田,三木,水町,石森: Bull.Chom.Soc.Jpm. 61. 594-596 (1988)

    • Related Report
      1987 Annual Research Report
  • [Publications] 鎌田,小西,三木,石森: Chem.Lett. 159-162 (1988)

    • Related Report
      1987 Annual Research Report
  • [Publications] 伊藤,水町: Inorg.Chem.

    • Related Report
      1987 Annual Research Report
  • [Publications] 立屋敷,水町,長尾: Chem.Lett.

    • Related Report
      1987 Annual Research Report
  • [Publications] 斎藤,吉野,藤本,水町: "分析化学" 裳幸房, 370 (1988)

    • Related Report
      1987 Annual Research Report
  • [Publications] 三木,田中,水町,石森: Bull.Chem.Soc.Jpn.59. 3275-3276 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 鎌田,木村,広田,三木,水町,石森: Bull.Chem.Soc.Jpn.60. 1343-1347 (1987)

    • Related Report
      1986 Annual Research Report
  • [Publications] 福地,長尾,三木,水町,石森: Bull.Chem.Soc.Jpn.

    • Related Report
      1986 Annual Research Report
  • [Publications] 伊藤,水町: Bull.Chem.Soc.Jpn.

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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