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1997 Fiscal Year Final Research Report Summary

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)

Project Period (FY) 1995 – 1997
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.

  • Research Products

    (24 results)

All Other

All Publications (24 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 1999-03-16  

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