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Stereoselective Formation and Chemical Properties of Chiral Polynuclear Complexes Depending on Oxidation Numbers

Research Project

Project/Area Number 14540510
Research Category

Grant-in-Aid for Scientific Research (C)

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) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2002: ¥2,000,000 (Direct Cost: ¥2,000,000)
KeywordsS-Bridged Complexes / Electric Redox Behavior / Spectroelectrochemistry / Spectrochemistry / Stereochemistry
Research Abstract

The UV-vis spectroelectrochemical properties of S-bridged tricobalt(III) complexes [Co^<III>{Co^<III>(aet or L-cys)_3}_2]^<3+ or 3-> and dicobalt(III) complexes [Co^<III>{Co^<III>(aet or L-cys)_3}(dien)]^<3+ or 0> (aet = 2-aminoethanethiolate, L-cys = L-cysteinate, dien = diethylenetriamine) were investigated using a thin-layer quartz cell with a platinum mesh working electrode. The absorption spectroelectrochemical measurements for the tricobalt(III) complexes indicated that a two-electron reduction proceeds through pseudo two-steps, Co^<III>Co^<III>Co^<III>→Co^<III>Co^<II>Co^<III>→Co^<III>Co^<II>Co^<II> for the aet complex, while through pseudo one-step for the L-cys complex. The CD spectroelectrochemical measurements demonstrated that the optically active isomer (ΔΔ form) of the aet tricobalt(III) complex loses chirality during the one-electron reduction, whereas the Δ_<LLL>Δ_<LLL> isomer of the L-cys tricobalt(III) complex is reduced with an inversion of configuration, to form the Λ_<LLL>Λ_<LLL> isomer. The Λ_<LLL>Λ_<LLL> isomer is reduced with a retention of configuration. The aet and L-cys dicobalt(III) complexes were converted to the corresponding tricobalt(III) complexes by electrochemical reduction, accompanied by the release of the Co(II) ion and dien ligand. It was also elucidated that this conversion occurred with a retention of configuration.
Similar properties and reactivities have been studied for the polynuclear complexes with various metal ions and organic ligands.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] 岡本健一 他4名の共著: "Characterization and electrochemical properties for rhenium(III) ion incorporated into linear-type S-bridged trinuclear complexes."Polyhedron. 21. 1809-1816 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 岡本健一 他5名の共著: "UV-Vis Absorption and CD Spectroelectrochemical Studies on S-Bridged Polycobalt(III) Complexes with 2-Aminoethanethiolata or L-Cysteinate"Bulletin of the Chemical Society of Japan. 76. 1191-1197 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 岡本健一 他4名の共著: "Optically Active Sulfur-Bridged Co(III)-M(II) (M = Pd, Pt) Dinuclear Complexes with Square-Planar [M(μ-S)2(bpy)] (bpy = 2,2'-bipyridine) Frameworks Derived from..."Polyhedron. 22. 1507-1513 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Mahboob, Y.Miyashita, Y.Yamada, K.Fujisawa, K.Okamoto: "Characterization and Electrochemical Properties for Rhenium(III) Ion Incorporated into Linear-type S-Bridged Trinuclear Complexes. Crystal Structures of ΔΔ-and ΔΔ/ΔΔ-[Re{Ir(aet)_3}_2]^<3+> (aet=2-Aminoethanethiolate)"Polyhedron. 21. 1809-1816 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Miyashita, H.Yoshida, T.Sato, Y.Yamada, K.Fujisawa, K.Okamoto: "UV-Vis Absorption and CD Spectroelectrochemical Studies on S-Bridged Polycobalt(III) Complexes with 2-Aminoethanethiolate or L-Cysteinate"Bull.Chem.Soc.Jpn.. 76. 1191-1197 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Yamada, M.Uchida, M.Fujita, Y Miyashita, K.Okamoto: "Optically Active Sulfur-Bridged Co(III)-M(II) (M=Pd, Pt) Dinuclear Complexes with Square-Planar [M(m-S)_2(bpy)] (bpy=2,2'-bipyridine) Frameworks Derived from Octahedral Bidentate Sulfur-Donating Co(III) Metalloligands"Polyhedron. 22. 1507-1513 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 岡本健一 他5名の共著: "UV-Vis Absorption and CD Spectroelectrochemical Studies on S-Bridged"Bulletin of the Chemical Society of Japan. 76. 1191-1197 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 岡本健一 他4名の共著: "Optically Active Sulfur-Bridged Co(III)-M(II) (M=Pd, Pt) Dinuclear Complexes with"Polyhedron. 22. 1507-1513 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 岡本健一 他5名の共著: "UV-Vis Absorption and CD Spectroelectrochernical Studies on S-Bridged Polycobalt (III) Complexes with 2-Aminoethanethiolate or L-Cysteinate"Bulletin of the Chemical Society of Japan. 76(印刷中). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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