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Strucural Conversion of Sulfur-Bridged Polynuclear Complexes by Metal Replacement Reaction

Research Project

Project/Area Number 09640658
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionGUNMA UNIVERSITY

Principal Investigator

KONNO Takumi  Gunma University, Chemistry, Professor, 工学部, 教授 (50201497)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1997: ¥2,500,000 (Direct Cost: ¥2,500,000)
KeywordsS-Bridged Polynuclear Complex / Strcutural Conversiton / Palladium(II) Ion / Thiolate Ligand / Silver(I) Ion / Zinc(II) Ion / Cobalt(III) Complex / Single-Crystal X-ray Analysis / らせん構造 / 光学分割 / チオレート配位子 / 分子集合体
Research Abstract

The aggregation of octaetal complexes with two or three thiolate ligands assisted by metal ions has been shown to form a variety of S-bridged polynuclear complexes containing several chiral centers. It has been noted that the structures of these polynuclear complexes are highly dependent on the coordination geometry of metal ions incorporated with the octahedral complexes. In order to better understand the properties characteristic of the S-bridged structure of this type, it is necessary to investigate analogous S-bridged polynuclear complexes composed of (tris)- or (bis)thiolato complex-units.
In this study, we have found that the novel S-bridged Co^<III>Ag^I_3Co^<III> pentanuclear complexes, [Ag_3{Co(aet) _3}_2] ^<3+> and [Ag_3{Co(L-cys-N,S) _3}_2, ] ^<3->, were prepared by reacting fac(S)-[Co(aet or L-cys-N,S) _3] ^<0or3-> with linear Ag^+. In the Co^<III>Ag^I_3Co^<III>structure, the two thiolato S atoms from two fac(S)-[Co(aet or L-cys-N,S) _3] ^<0or3-> units coordinate to each of three Ag atoms, such that the three S-Ag-S linkages form a triple helical structure, On the other hand, the reaction of an S-bridged Co^<III>Ni^<II>Co^<III> trinuclear complex, [Ni{Co(aet) _2 (en)}_2]Cl_4, with Na_2 [PdCI_4 ] in a ratio of 1 : 1 gave an S-bridged Co^<III>Pd^<II>Co^<III> trinuclear complex, [Pd{Co(aet) _2 (en)}_2]Cl_4, while the corresponding 1 : 2 reaction produced an S-bridged Co^<III>Pd^<II> dinuclear complex, [PdCl_2{Co(aet) _2 (en)}]CI.In the Co^<III>Pd^<II>Co^<III> structure the Pd^<II> atom is coordinated by four S atoms from two cis(S)-[Co(aet) _2 (en)] ^+ units, while the Pd_<II> atom in the Co_<III>Pd_<II> structure is coordinated by two Cl atoms besides two S atoms from one octahedral unit.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] 今野、後藤、岡本: "Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co_2(aet)_2}{Co(aet)_3}_2]^<4+>" Inorganic Chemistry. 36・22. 4992-4997 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 今野、町田、岡本: "Novel S-Bridged Co^<III>Pd^<II> Pentanuclear Complexes Derived from [Ni^<II>{Co^<III>(aet)_2(en)}_2]Cl_4(aet=2-Aminoethanethiolate)" Bulletin of the Chemical Society of Japan. 71・1. 175-181 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 今野、徳田、鈴木、岡本: "Preparation and Properties of S-Bridged Co^<III>Ag^ICo^<III> Pentanuclear Complexes Having a Triple Helical Chirality" Bulletin of the Chemical Society of Japan. 71・5. 1049-1054 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 岡本、吉成、坂上、今野: "Synthesis, Crystal Structures, and Oroperties of S-Briged Pt(II)-Ni(II)Dinuclear Complexes" Bulletin of the Chemical Society of Japan. 71・6. 1363-1371 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Konno, Y.Goto, and K.Okamoto: "Synthesis, Crystal Structures, and Spectroscopic Characterization of Two Pairs of Racemic Isomers of [{Co_2(aet)_2}{Co(aet)_3}_2]^<4+>(aet=2-Aminoethanethiolate) : A Novel S-bridged Tetranuclear Cobalt(III) Complex Formed by Ligand Transfer from Nickel(II) to Cobalt(III)" Inorganic Chemistry. 36-22. 4992-4997 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Konno, T.Machada, and K.Okamoto: "Novrel S-Bridged Co^<III>Pd^<II>Polynuclear Complexes Derived form [Ni^<II>{Co^<III>(aet)_2(en)}_2Cl_4(aet=2-Aminoethanethiolate).Crystal Structures of [Pd{Co(aet)_2(en)}_2]Cl_4 and [PdCl_2{Co(aet)_2(en)}]Cl" Bulletin of the Chemical Society of Japan. 71-5. 175-181 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Konno, K.Tokuda, T.Suzuki, and K.Okamoto: "Preparation and Properties of S-Bridged Co^<III>Ag^I_3Co^<III> Pentanuclear Complexes Having a Triple Helical Chirality.Crystal Structure of [Ag_3{Co(aet)_3}_2](BF_4)_3(aet=2-Aminoethanethiolate)" Bulletin of the Chemical Society of Japan. 71-5. 1049-1054 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 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 an S-Bridged Structure with Pt(II)(aet=2-Aminoethanethiolate)" Bulletin of the Chemical Society of Japan. 71-6. 1363-1371 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 今野、徳田、鈴木、岡本: "Preparation and Properties of S-Bridged Co^<III>Ag^ICo^<III> Pentanuclear Complexes Having a Triple Helical Chirality" Bulletin of the Chemical Society of Japan. 71・5. 1049-1054 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 今野、町田、岡本: "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・1. 175-181 (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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