• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

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

Research Project

Project/Area Number 07640736
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

KONNO Takumi  University of Tsukuba, Chemistry, Assistant Professor, 化学系, 講師 (50201497)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsS-Bridged Polynuclear Complex / Strcutural Conversiton / Trigonal-bipyramidal Structure / Thiolate Ligand / Cadmium (II) Ion / Cobalt (III) Complex / Molecular Aggregation / Single-Crystal X-ray Analysis / 平面性金属イオン / 異常結合 / 配位子転移 / 自然分晶 / 絶対配置 / 結晶構造
Research Abstract

Coordinated thiolato S atoms in mononuclear Co (III) complexes have been recognized to bind with other metal ions to form S-bridged polynuclear complexes. In fact, considerable progress has been made in the chemistry of S-bridged polynuclear complexes containing [Co (aet) (en) _2] ^<2+> or fac (S) - [Co (aet) _3] units (aet=2-aminoethanethiolate, en=ethylenediamine). On the other hand, no S-bridged polynuclear complexes containing [Co (aet) _2 (en)] ^+ units have long been studied, because of the difficulty in preparation of [Co (aet) _2 (en)] ^+ used as a starting mononuclear complex. We have recently found that the facile reaction of [Ni (aet) _2] with [CoCl_2 (en) _2] ^+ gives an S-bridged CO^<III>Ni^<II>Co^<III> trinuclear complex, [Ni {Co (aet) _2 (en)} _2] ^<4+> (1), in which the central Ni^<II> atom is coordinated by four Satoms from two C_2-cis (S) - [Co (aet) _2 (en)] ^+ units. In order to better understand the chemistry of S-bridged polynuclear complexes composed of octahedra … More l thiolato units, it is desirable to investigate other S-bridged polynuclear complexes composed of [Co (aet) _2 (en)] ^+ units.
In the present study, it was found that the replacement of the Ni^<II> atom in [Ni {Co (aet) _2 (en)} _2] Cl_4 is achieved by the reaction with excess CdCl_2 in water. However, the reaction product was not a corresponding S-bridged Co^<III>Cd^<II>Co^<III> trinuclear complex [Cd {Co (aet) _2 (en)} _2] ^<4+>, but a neutral dinuclear complex [CdCl_3 {Co (aet) _2 (en)}] (2), in which the Cd atom is situated in a trigonal-bipyramidal environment. When 2 was treated with a large amount of NaNO_3 in water, a cationic Co^<III>_4Cd^<II>_2 hexanuclear complex [Cd_2Cl {Co (aet) _2 (en)} _4] ^<7+> (3) was produced. In 3 each Cd^<II> atom also adopts a trigonal-bipyramidal geometry, coordinated by a bridging Cl atom besides four S atoms from the two C_2-cis (S)- [Co (aet) _2 (en)] ^+ units. Attempts to remove the bridging Cl atom from 3 by treating with a large amount of NaNO_3 in water were unsuccessful. Accordingly, it is reasonable to assume that the Co^<III>Cd^<II> polynuclear structures composed of C_2-cis (S) - [Co (aet) _2 (en)] ^+ units are stabilized by the preference of Cd (II) for the trigonal-bipyramidal geometry. The large covalent radius of the Cd^<II> atom and the small S-Cd-S bite angle restricted by the C_2-cis (S) - [Co (aet) _2 (en)] ^+ metalloligand seem to be responsible for this geometrical preference. Less

Report

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

    (9 results)

All Other

All Publications (9 results)

  • [Publications] 今野、佐々木、岡本: "Novel Aggregation of fac(S)-[Rh(aet)_3] by Square-Planar Palladium(II)" Chemistry Letters. 977-978 (1996)

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

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 今野、岡本: "Stoichiometric Interconversion of S-Bridged Rh^<III>_2Ag^I_3 Pentanuclear and Rh^<III>_4Ag^I_5 Nonanuclear Structure" Inorganic Chemistry. 37. (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 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) (aet=2-Aminoethanethiolate, en=Ethylenediamine)" Chemistry Letters. 975-976 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Konno, S.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 Penatnuclear Complex [Pd {Pd (aet)} {Rh (aet) _2} {Rh (aet) _3} _2] Br_4 (aet=2-Aminoethanethiolate)" Chemistry Letters. 977-978 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Konno and K.Okamoto: "Stoichiometric Interconversion of S-Bridged Rh^<III>_2Ag^I_3 Pentanuclear and Rh^<III>_4Ag^I_5 Nonanuclear Structure : Synthesis and Structural Characterization of [Ag_3 {Rh (aet) _3} _2] ^<3+> and [Ag_5 {Rh (aet) _3} _4 ] ^<5+> (aet=2-Aminoethanethiolate)" Inorganic Chemistry. 36 in press. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 今野、佐々木、岡本: "Novel Aggregation of fac(S)-[Rh(aet)_3]by Square-Planar Palladium(II)" Chemistry Letters. 977-978 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 今野、岡本: "Synthesis,Structural Characterization,and Interconversion of S-Bridged Dinuclear and Hexanuclear Complexes of cis(S)-[Co(aet)_2(en)]^+" Chemistry Letters. 975-976 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 今野、岡本: "Stoichiometric Interconversion of S-Bridged Rh^<III>_2Ag^I_3Pentanuclear and Rh^<III>_4Ag^I_5 Nonanuclear Structure" Inorganic Chemistry. 37(in press). (1997)

    • Related Report
      1996 Annual Research Report

URL: 

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

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi