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Study on Novel Binuclear Heteronuclear Mixed-valence Complexes

Research Project

Project/Area Number 04640488
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionSaitama University

Principal Investigator

SATO Masaru  Chemical Analysis Center, 分析センター, 助教授 (90008863)

Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1993: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1992: ¥1,600,000 (Direct Cost: ¥1,600,000)
Keywordsferrocenylacetylene / ruthenocenylacetylene / binuclear complex / mixed-valence complex / pentametylruthenocene
Research Abstract

From the viewpoint exploring the mechanism for induction of the functionality, e.g.electro-conductivity, in organometallic compounds, various transition-metal metallocenylacetylide complexes were examined.
1. Ru(II) ferrocenylacetylide complexes were synthesized and their one-electron oxidized complexes were successfully isolated. The structure of the complex was confirmed by X-ray analysis. It was shown by various spectral data that there was large electron-delocalization in these complexes.
2. Fe(II) ferrocenylacetylide complexes were synthesized by the metal-exchange reaction. In the one-electron exidized complexes the oxidized site was localized on the Fe atom of ferrocenyl moiety and the electron-delocalization between two Fe atoms was small.
3. Phosphine-coordinated Fe(II) ferrocenylacetylide complexes were synthesized by photo-irradiation in presence of bisphosphines. It was clear by various spectral data that there was large electron-delocalization in these one-electron oxidized complexes. The charge-transfer complex with DDQ, TCNQ, etc showed the electron-elocalization according with the electron-withdrowing ability of acceptor.
4. Pt(II) ferrocenylacetylide complexes were prepared in the reaction of ferrocenylacetylene with the chloroplatinum complexes. In the one-electron oxidized complexes there was a little electron-delocalization.
5. Ru(II) ruthenocenylacetylide complexes were prepared in the reaction of ruthenocenylacetylene with the chlororuthenium complexes. In the complexes stable two-electron oxidized complexes was isolated, because of the spin-pairing of the unpaied-electron on both the Ru atoms. Ru(II) pentamethyl-ruthenocenylacetylide complexes were also prepared.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] M.Sato,M.Asai: "Synthesis and Some Properties of Diferrocenylthioketones and Dynamic Behavior of Some〔1.1〕ferrocenophane Derivatives" Journal of Organometallic Chemistry. 430. 105-110 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sato,M.Sekino: "Synthesis and Properties of Ruthenium Vinylidene and Acetylide Complexes containing 1,1'-Bis(diphenylphosphino)ferrocene" Journal of Organometallic Chemistry. 444. 185-190 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sato,H.Asano,S.Akabori: "Novel Dimeric Stracture in the Pd(11)Complex of 1,10-dithia〔2〕(2.6)-pyridino〔2〕(1.1')ferrocenophane.A Connected Metal-metal Interaction" Journal of Organometallic Chemistry. 452. 105-109 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sato,H.Shigeta,M.Sekino,S.Akabori: "Synthesis,Some Reactions,and Molecular Structure of the Pd(BF_4)_2 Complex of 1.1'-Bis(diphenylphosphino)ferrocene" 458. 199-204 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sekino,M.Sato,A.Nagasawa,K.Kikuchi: "Tungsten Carbyne Complexes Containing 1.1'-Bis(diphenylphosphino)ferrocene(dppf).Reverse Relationship between NMR Chemical Shifts of Carbyne ^<13>C and ^<123>W Nuclei and…" Organometallics. 13(in press). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sato,H.Shintate,Y.Kawata,M.Sekino,…: "Oxidized Ruthenium Ferrocenylacetylide Complexes,[(η-C_5H_5)L_2RuCCFc]-PF_6 or [(η-C_5Me_5)L_2RuCCFc]PF_6(L=phosphine).Well Electron-delocalized Heteronuclear Mixed-valence Complexes" Orgamometallics. 13(in press). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Sato,H.Asano,S.Akabori: "Novel Dimeric Structure in the Pd(11)Complex of 1,10-dithia〔2〕(2,6)pyridino〔2〕-(1,1′)terrocenophane.A Connected Metal-metal Interaction" Journal of Organometallic Chemistry. 452. 105-109 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Sato,H.Shigeta,M.Sekino,S.Akabori: "Synthesis,some reactions,and molecular structure of the Pd(BF_4)_2 complex of 1,1′-bis(diphenylphosphino)ferrocene" Journal of Organometallic Chemistry. 458. 199-204 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Sekino,M.Sato,A.Nagasawa,K.Kikuchi: "Tungsten Carbyne Complexes Containing 1,1′-Bis(diphenylphosphino)ferrocene(dppf).Reverse Relationship between NMR Chemical Shifts of the Carbyne ^<13>C and ^<183>W Naclei and‥…" Organometallics. 13 in press. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Sato,H.Shintate,Y.Kawata,M.Sekino,‥‥: "Oxidized Ruthenium Ferrocenylacetylide Complexes,[(η-C_5H_5)L_2 Ru CC Fc]PF_6 or [(η-C_5Me_5)L_2 Ru CC Fc]PF_6(L=phosphine).Well Electron-delocalized Heteronuclear……" Organometallics. 13 in press. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Sato,M.Asai: "Synthesis and Some proherties of diferrocenylthioketones and dynamic behauion of some 〔1.1〕 ferrocenophane deruiratuies" Journal of Organonutallic Chemistry. 430. 105-110 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Sato,M.Sekino: "Synthessi and properties of ruthenuim vinylidene and acetylide complexes containing 1、1'-bis(diphenylphosphino)-ferrocene" Journal of Organometallic Chemistry. 444. 185-190 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Sato,H.Asano,S.Akabori: "Strange dimeric stwcture in the Pd(11) omplex of 1、10-dithia〔2〕(2、6)pyidino〔2〕(1、1')ferrocenoplane,A connected metal-nutal interaction" Journal of Organometallic Chemistry.

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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