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金属の結合様式に基づく硫黄架橋多核錯体の組織化と制御

Research Project

Project/Area Number 07454172
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

OKAMOTO Ken-ichi  University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (70132983)

Co-Investigator(Kenkyū-buntansha) 今野 巧  筑波大学, 化学系, 講師 (50201497)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1997: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1996: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1995: ¥4,100,000 (Direct Cost: ¥4,100,000)
KeywordsS-Bridged Complexes / Polynuclear Complexes / Stereochemistry of Complexes / Coordination Modes / Stereoselectivity / Systematization of Complexes / Control of Structures
Research Abstract

We have investigated the possibility of the selective formation for the polynuclear complexes, which are given by the reactions of the mononuclear complexes with various metal ions depending on the coordination modes. In this work, firstly, the chromium (III) ions or mononuclear complexes have been selected, since they take unpaired electrons, and poor stability and highly reactivity for the sulfur donor atoms. The selective aggregations of the octahedral chromium (III) complexes around the metal ions are performed and discussed in relation to the unpaired electrons and the interactions between the metal centers. The reactions of the octahedral complexes with the metal ions being the linear-type coordination modes gave stereoselectively the pentanuclear complexes. The reactions of the metal ions being possible for both of the linear-and tetrahedral-type coordination modes can give the pentanuclear and octanuclear complexes, respectively. Further, the cis complexes react with the palladium (II) ion to give the dinuclear complexes and trinuclear or hexanuclear complexes being square-planar complexes and trigonal-bipy-ramidal, whose structures are controlled by the chloride ions. When the square-planar complexes, in which the ligands are less susceptible to substirution of other ligands, reacts with the square-planar complexes, the dinuclear complexes are selectively formed without the hexanuclear complexes. Finally, the fairly stable dinuclear complexes with the disulfide bond are selectively formed by treating with suitable oxidation conditions for the octahedral mononuclear complexes. All of the stereoselectively obtained polynuclear complexes are studied in regard to the sterochemical, spectrochemical, electrochemical, and magnetic properties.

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (35 results)

All Other

All Publications (35 results)

  • [Publications] Takumi Konno: "First Conversion of a Square-planar [Ni(aet)_2] to an Octahedral [Ni(aet)_2L] by Forming S-Bridged Structure with Pt(II) (aet = 2-Aminoethanethiolate;L=(H_2O)_2 or 2,2´-Bipyridine)" ChemiStry Letters. 989-990 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Ken-ichi Okamoto: "Syntheses and Some Properties of S-Bridged pentanuclear Co(III)-Hg(II) or Rh(III)-Hg(II) Complexes with 2-Aminoethanethiolate. Crystal Structure of [{ Rh(aet)_3}_2(HgCl_2)_3]and [{Rh(aet)_3}_22Hg_3(N0_3)_4](N0_3)_2" Bulletin of the Chemical Society of Japan. 68. 2573-2580 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Kageyama: "Synthesis and Some Properties of T-Cage Type Co^<III>_4Hg^<II>_4 and Rh^<III>_4Hg^<II>_4 Octanuclear Complexes with 2-Aminoethanethiolate" Inorganica Chimica Acta. 239. 19-23 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takumi Konno: "Synthesis, Structural Characterization, and Interconversion of S-Bridged Dinuclear and Hexanuclear Complexes Composed of cis(S)-[Co(aet)_2(en)]^+ and Trigonal-Bipyramidal Cadmium(II)" Chemistry Letters. 975-976 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takumi Konno: "Novel Aggregation of fac(S)-[Rh(aet)_3] by Square-Planar Palladium(II): Crystal Structure of Spontaneously Resolved Rh^<III>_3Pd^<II>_2 Pentanuclear Complex [Pd{Pd(aet)}{Rh(aet)_2}{Rh(aet)_3}_2]Br_4" Chemistry Letters. 977-978 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takumi Konno: "Novel Dinuclear Iridium (III) Complex with a Bridging Disulfide Bond. Conversion of Coordinated Thiolato to Coordinated Bridging Disulfide by Acid Oxidation" Chemistry Letters. 85-86 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Ken-ichi Okamoto: "Synthesis, characterization and some properties of S-bridged polynuclear complexes composed of fac(S)-[Cr(aet)_3] units (aet=2-aminoethanethiolate)" Inorganica Chimica Acta. 260. 17-26 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takumi Konno: "Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of[{Co_2(aet)_2}{Co(aet)_3}_2]^<4+> and (aet=2-Aminoethanethiolate)" Inorganic Chemistry. 36. 4992-4997 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takumi Konno: "Novel S-Bridged Co^<III>Pd^<II>Polynuclear Complexes Derived from [Ni^<II>{Co^<III>(aet)_2(en)}_2]Cl_4(aet=2-Aminoethanethiolate)" Bulletin of the Chemical Society of Japan. 71. 175-181 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yoshitaro Miyashita: "Preparation, Stereochemistry, and Reactivity of Linear-Type S-Bridged MCr^<III>M(M=Rh^<III>,Ir^<III>) Trinuclear Complexes with 2-Aminoethanethiolate(aet)" Bulletin of the Chemical Society of Japan. 71. 661-670 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Ken-ichi Okamoto: "Synthesis, Crystal Structures, and Properties of S-Bridged Pt(II)-Ni(II) Dinuclear Complexes: Con-version of Square-planar [Ni(aet)_2] to Octahedral Geometry by Forming S-Bridged Structure with Pt(II)" Bulletin of the Chemical Society of Japan. 71. 1363-1371 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yoshitaro Miyashita: "Preparation, Characterization, and Some Properties of Novel Dinuclear Complexes with a Coordinated Bridging Disulfide Bond. Crystal Structures of △_R∧_S-[M_2(2-aminoethane-thiolato)_4(cystamine)]^<2+>(M=Ir^<III>,Rh^<III>)" Bulletin of the Chemical Society of Japan. 71(印刷中). (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno, Y.Yoshinari, and K.Okamoto: "First Conversion of a Square-planar [Ni (aet)_2] to an Octahedral [Ni(aet)_2L] by Forming S-Bridged Structure with Pt (II) (aet=2-Aminoethanethiolate ; L=(H_2O)_2 or 2,2'-Bipyridine)" Chem.Lett.989-990 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Okamoto, Y.Kageyama, and T.Konno: "Syntheses and Some Properties of S-Bridged pentanuclear Co (III) -Hg (II) or Rh (III) -Hg (II) Complexes with 2-Aminoethanethiolate. Crystal Structure of [{Rh(aet)_3}_2(HgCl_2)_3] and [{Rh(aet)_3}_2Hg_3(NO_3)_4] (NO_3)_2" Bull.Chem.Soc.Jpn.68. 2573-2580 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Kageyama, T.Konno, K.Okamoto, and J.Hidaka: "Synthesis and Some Properties of T-Cage Type Co^<III>_4Hg^<II>_4 and Rh^<III>_4Hg^<II>_4 Octanuclear Complexes with 2-Aminoethanethiolate" Inorg.Chim.Acta. 239. 19-23 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno and K.Okamoto: "Synthesis, Structural Characterization, and Interconversion of S-Bridged Dinuclear and Hexanuclear Complexes Composed of cis (S) - [Co(aet)_2(en)]^+ and Trigonal-Bipyramidal Cadmium (II)" Chem.Lett.975-976 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno, C.Sasaki, and K.Okamoto: "Novel Aggregation of fac (S) - [Rh(aet)_3] by Square-Planar Palladium (II) : Crystal Structure of Spontaneously Resolved Rh^<III>_3Pd^<II>_2 Pentanuclear Complex [Pd{Pd(aet)} {Rh(aet)_2} {Rh(aet)_3}_2] Br_4" Chem.Lett.977-978 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno, Y.Miyashita, and K.Okamoto: "Novel Dinuclear Iridium (III) Complex with a Bridging Disulfide Bond.Conversion of Coordinated Thiolato to Coordinated Bridging Disulfide by Acid Oxidation" Chem.Lett.85-86 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Okamoto, M.Matsumoto, Y.Miyashita, N.Sakagami, J.Hidaka, and K.Konno: "Synthesis, characterization and some properties of S-bridged polynuclear complexes composed of fac (S) - [Cr (aet)_3] unit (aet=2-aminoethanethiolate)" Inorg.Chim.Acta. 260. 17-26 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno, Y.Gotoh, and K.Okamono: "Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co_2(aet)_2} {Co(aet)_3}_2]^<4+> and (aet=2-Aminoethanethiolate)" Inorg.Chem.36. 4992-4997 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Konno, T.Machida, and K.Okamoto: "Novel S-Bridged Co^<III>Pd^<II> Polynuclear Complexes Derived from [Ni^<II>{Co^<III>(aet)_2(en)}_2] Cl_4 (aet=2-Aminoethanethiolate)" Bull.Chem.Soc.Jpn.71. 175-181 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Miyashita, N.Sakagami, Y.Yamada, T.Konno, J.Hidaka, and K.Okamoto: "Preparation, Stereochemistry, and Reactivity of Linear-Type-S-Bridged MCr^<III>M (M=Rh^<III>, Ir^<III>) Trinuclear Complexes with 2-Aminoethanethiolate (aet)" Bull.Chem.Soc.Jpn.71. 661-670 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Okamoto, Y.Yoshinari, Y.Yamada, N.Sakagami, and T.Konno: "Synthesis, Crystal Structures, and Properties of S-Bridged Pt (II) -Ni (II) Dinuclear Complexes : Conversion of Square-planar [Ni(aet)_2] to Octahedral Geometry by Forming S-Bridged Structure with Pt (II)" Bull.Chem.Soc.Jpn.71. 1363-1371 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Miyashita, N.Sakagami, Y.Yamada, T.Konno, and K.Okamoto: "Preparation, Characterization, and some Properties of Novel Dinuclear Complexes with a Coordinated Bridging Disulfide Bond. Crystal structures of DELTA_RLAMBDA_S [M_2(2-aminoethanethiolate)_4(cystamine)]^<2+> (M=Ir^<III>, Rh^<III>)" Bull.Chem.Soc.Jpn.71(in press). (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Ken-ichi Okamoto: "Synthesis,characterization and some properties of S-bridged polynuclear complexes composed of fac(S)-[Cr(aet)_3] units (aet = 2-aminoethanethiolate)." Inorganica Chimica Acta. 260. 17-26 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takumi Konno: "Synthesis,Crystal Structures,and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co_2(aet)_2}{Co(aet)_3}_2]^<4+> and (aet = 2-Aminoethanethiolate)" Inorganic Chemistry. 36. 4992-4997 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takumi Konno: "Novel S-Bridged Co^<III>Pd^<II> Polynuclear Complexes Derived from [Ni^<II>{Co^<III>(aet)_2(en)}_2]Cl_4 (aet = 2-Aminoethanethiolate)" Bulletin of the Chemical Society of Japan. 71. 175-181 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Ken-ichi Okamoto: "Synthesis,Crystal Structures,and Properties of S-Bridged Pt(II)-Ni(II) Dinuclear Complexes : Conversion of Square-planar [Ni(aet)_2] to Octahedral Geometry by Forming S-Bridged Structure with Pt(II)" Bulletin of the Chemical Society of Japan. 71(印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Yoshitaro Miyashita: "Preparation,Stereochemistry,and Reactivity of Linear-Type S-Bridged MCr^<III>M (M = Rh^<III>,Ir^<III>) Trinuclear Complexes with 2-Aminoethanethiolate (aet)" Bulletin of the Chemical Society of Japan. 71(印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Kageyama: "Synthesis and Some Properties of T-Cage Type Co^<III>_4Hg^<II>_4 and Rh^<III>_4Hg^<II>_4 Octanuclear Complexes with 2-Aminoethanethiolate" Inorganica Chimica Acta. 239. 19-23 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Konno: "Synthesis,Structural Characterization,and Interconversion of S-Bridged Dinuclear and Hexanuclear Complexes Composed of cis(S)-[Co(aet)_2(en)]^+and Trigonal-Bipyramidal Cadmium(II)" Chemistry Letters. 975-976 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Konno: "Novel Aggregation of fac(S)[Rh(aet)_3]by Square-Planar Palladium(II) : Crystal Structure of Spontaneously Resolved Rh^<III>_3Pd^<II>_2 Pentanuclear Complex[Pd{Pd(aet)}{Rh(aet)_2}{Rh(aet)_3}_2]Br_4" Chemistry Letters. 977-978 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Konno: "Novel Dinuclear Iridium(III)Complex with a Bridging Disulfide Bond. Conversion of Coordinated Thiolato to Coordinated Bridging Disulfide by Acid Oxidation21GC04:Chemistry Letters" 85-86 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takumi Konno: "First Conversion of a Square-planar [Ni(aet)_2]to an Octahedral [Ni(aet)_2L]by Forming S-Bridged Structure with Pt(II)(aet=2-Aminoethanethiolate ; L=(H_2O)_2 or 2, 2′-Bipyridine)" Chemistry Letters. 989-990 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Ken-ichi Okamoto: "Syntheses and Some Properties of S-Bridged pentanuclear Co(III)-Hg(II) or Rh(III)-Hg(II)Complexes with 2-Aminoethanethiolate.Crystal Structure of [{Rh(aet)_3}_2(HgCl_2)_3] and [{Rh(aet)_3}_2Hg_3(NO_3)_4](NO_3)_2" Bulletin of the Chemical Society of Japan. 68. 2573-2580 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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