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金属錯体ユニットの合理的組み替えとキラリティーの自在制御

Research Project

Project/Area Number 16033235
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka University

Principal Investigator

今野 巧  大阪大学, 理学研究科, 教授 (50201497)

Project Period (FY) 2004 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥4,300,000 (Direct Cost: ¥4,300,000)
Fiscal Year 2005: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2004: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywords多核金属錯体 / 錯体ポリマー / チオール配位子 / コバルト(III) / 金(I) / 錯体配位子 / キラリティー / 硫黄架橋金属錯体 / 金属超分子 / チオレート型配位子 / ロジウム(III) / ニッケル(II)
Research Abstract

本研究では、チオラト基のほかにカルボキシル基やアミノ基をもつ単核および多核錯体の合成、これらのチオラト錯体と各種金属イオンとの反応による異種金属多核錯体や錯体ポリマーの合成、ならびに単核ユニットの組み替えによる構造変換について検討した。
その結果、L-システインをN,S-二座で配位したコバルト(III)単核錯体([Co(L-cys-N,S)(en)_2]^+)と銀(I)およびマンガン(II)イオンとの段階的反応から梯子状構造をもつCo^<III>_4Mn^<II>_3Ag^I_2錯体ポリマーを、金(I)およびマンガン(II)イオンとの段階的反応からディスクリートなCo^<III>_2Mn^<II>Au^I四核錯体および鎖状構造をもつCo^<III>_2Mn^<II>Ag^I錯体ポリマーを、さらには銅(I)およびカドミウム(II)イオンとの段階的反応から2次元ハニカム構造をもつCo^<III>_3Cd^<II>_3Cu^I錯体ポリマーを得た。これにより、[Co(L-cys-N,S)(en)_2]^+が配位チオラト基およびフリーのカルボキシル基を用いて性質の異なる金属イオンに配位するキラルな錯体配位子として機能することが示された。一方、D-ペニシラミンを硫黄単座で2分子配位した金(I)酸錯体([Au(D-pen-S)_2]^<3->)とニッケル(II)イオンとの反応からは、反応モル比やpHを変えることにより、互いに構造変換可能な、しかも性質(色、磁性、キラリティー)の異なる4種の多核錯体が形成されることを見出した。これにより、[Au(D-pen-S)_2]^<3->が柔軟に配位座を変えうる多座の錯体配位子として機能することが示された。

Report

(2 results)
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (12 results)

All 2006 2005 2004 Other

All Journal Article (12 results)

  • [Journal Article] Linear-Type S-Bridged Triruthenium Complexes with Aliphatic Aminothiolate Ligands : Synthesis, Characterization, and Properties2006

    • Author(s)
      松浦 紀之
    • Journal Title

      Inorganic Chemistry 45

      Pages: 401-408

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Conversion of 2-Aminoethanethiolate (aet) to 2-Benzoylaminoethanethiolate (L) in a S-Bridged Diruthenium(II) Complex Composed of Two cis-[Ru(bpy)_2] Units2006

    • Author(s)
      松浦 紀之
    • Journal Title

      Bulletin of The Chemical Society of Japan 79

      Pages: 297-299

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A Remarkable Co^<III> Mn^<II> Ag^I Heterometallic Aggregates with L-Cysteinate That Accommodate Chiral Cobalt(III) Octahedra in a ID Channel2005

    • Author(s)
      有冨 隆志
    • Journal Title

      Chemistry Letters 34

      Pages: 770-771

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Sulfur-bridged Linkage of [Ni(thiolato)_2(amine)_2]-type Complexes with Linear Gold(I) Ions Assisted by Aurophilic Interaction2005

    • Author(s)
      今野 巧
    • Journal Title

      Chemistry Letters 34

      Pages: 1146-1147

    • NAID

      10016649244

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Meso and Racemic Isomers of a New S-Bridged Diruthenium(II) Complex with Pendant Aminoalkyl Group2005

    • Author(s)
      松浦 紀之
    • Journal Title

      Chemistry Letters 34

      Pages: 1252-1253

    • Related Report
      2005 Annual Research Report
  • [Journal Article] The First Ru^<II>Pd^<II>_2S_3 Metallochelate Ring Formed on a [Ru(bpy)_2]^<2+> Core2005

    • Author(s)
      吉村 崇
    • Journal Title

      Chemistry Letters 34

      Pages: 1310-1311

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Aggregation of Octahedral Thiolato Complexes by Forming Sulfur-Bridged Structures with Transition Metal Ions2004

    • Author(s)
      今野巧
    • Journal Title

      Bulletin of The Chemical Society of Japan 77

      Pages: 627-649

    • NAID

      10012848560

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Sulfur-Bridged Co^<III>pt^<II>Co^<III> Trinuclear Complexes with Mixed Aliphatic and Aromatic Thiolate Ligands: Effect of Non-Bridging Ligands on the Homochiral Linkage of Cobalt(III) Octahedrons by Platinum(II)2004

    • Author(s)
      広津昌和
    • Journal Title

      Inorganic Chemistry 43

      Pages: 4406-4414

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Novel Aggregation of [Ni(thiolato)_2(amine)_2]-Type Square Planes Assisted by Silber(I) Ions2004

    • Author(s)
      今野巧
    • Journal Title

      Chemical Communication 2004-20

      Pages: 2296-2297

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis, Characterization, and Stereochemistry of S-Bridged Co^<III>MCo^<III>(M=Pd^<II>, Pt^<II>) Trinuclear Complexes Containing Two Non-bridging Thiolato Groups: Building Blocks for the Construction of Chiral Heterometallic Aggregates.2004

    • Author(s)
      近本悠
    • Journal Title

      Dalton Transaction 2004-21

      Pages: 3654-3661

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Rock-Salt Like Lattice Structure Consisting of Monocationic and Monoanionic An^IAg^ICu^<II> Supramolecular Cages of D-Penicillaminate2004

    • Author(s)
      豊田敦志
    • Journal Title

      Angewandte Chemie International Edition 44

      Pages: 1088-1092

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Two Stereoisomers of an S-Bridged Rh^<III>_2Pt^<II>_2 Tetranuclear Complex [{Pt(NH_3)_2}_2{Rh(aet)_3}_2]^<4+> That Lead to a Discrete and a 1D Rh^<III>_2Pt^<II>_2Ag^I Structures by Reacting with Ag (aet=2-Aminoethanethiolate)

    • Author(s)
      近本悠
    • Journal Title

      Inorganic Chemistry (印刷中)

    • Related Report
      2004 Annual Research Report

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Published: 2004-04-01   Modified: 2018-03-28  

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