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Electrochemical Studies of Phosphine and Arsine Complexes

Research Project

Project/Area Number 03453047
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionNagoya University

Principal Investigator

FUJITA Jun-nosuke  Nagoya Univ., Chem., Prof., 理学部, 教授 (80004266)

Co-Investigator(Kenkyū-buntansha) KITA M  Nagoya Univ., Chem., Res. Associate, 理学部, 助手 (20177827)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1992: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1991: ¥4,100,000 (Direct Cost: ¥4,100,000)
KeywordsPhosphine Complex / Arsine Complex / Electrochemistry / Co(III) Complexes
Research Abstract

A large number of phosphine and arsine complexes of a Lewis hard metal ion, Co(III) have been prepared, and their structure determination including X-ray analysis, and spectroscopic, photo- and electro-chemical studies have been carried out. The Co(III) complexes have, in general,filled dpi^6 (HOMO) and vacant dsigma (LUMO) orbitals, and thier energies approximately correspond, respectively, to oxidation and reduction potentials of the complexes. These potentials were largely dependent on the charge of complex ion, but the potential differences between them showed a good linear relation with transition energies of the first ligand field band. Thus one can estimate the dsigma and dpi energies of Co(III) complexes from the electro-chemical and absorption spectral data, and can discuss the donor and acceptor properties of ligands. From measurements of a number of amine, phosphine, and arsine complexes of the same type, it was concluded that the sigma-donor properties increase in the order of -PMe_2>-NH_2, -AsMe_2>-NMe_2. The dpi orbital energies were concluded to be destabilized in the order of -PMe_2>-AsMe_2>-NH_2,-NMe_2 by the pi-type donation of these coordination groups. Phosphine and arsine ligands seem to act as a pi-donor rather than a pi-acceptor towards hard metals such as Co(III) and destabilize the dpi orbitals of the metal ion.
The cis-[Co(dtc)_2{P(OR)_3}_2]^+-type complexes(dtc=dithiocarbamate ion) isomerized to the trans isomer by exposure of ultraviolet light in solution, but regenerated the original cis isomer in the dark. The isomerization also occured by electrochemical reduction to Co^<2+> and Co^+to give a equilibrium mixture of cis and trans isomers. No such isomerization properties were observed for the corresponding phosphine complexes.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] T.Suzuki and J.Fujita: "Preparati on and Characterization of Palladium(I) and Platinum(I) Dinuclear Complexes Bridged by 2-(Dimethylphosphino)pyridine" Bull.Chem.Soc.Jpn.65. 1016-1025 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki,N.IItaka,S.Kurachi,M.Kita,K.Kashiwabara,S.Ohaba,and J.Fujita: "Molecular Structures of TH-[MM'Cl_2(Me_2Ppy)_2](MM'=Pd_2PdPt and Pt_2)and HT-[Pd_2Cl_2(Ph_2Ppy)_2]" Bull.Chem.Soc.Jpn.65. 1817-1824 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Adachi,M.Kita,K.Kashiwabara,J.Fujita,N.IItaka,S.Kurachi,and S.Ohba: "Preparation and Characterization of Cobalt(III) Complexes Containing dppf or dmpf as a Bidentate Ligand,and Molecular Structures of [CoL_2(dmpf)BPh_4 L=acac and dtc" Bull.Chem.Soc.Jpn.65. 2037-2044 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,T.Yamamoto,K.Kashiwabara,and J.Fujita: "Bis[2-(dimethylphosphino)ethane-1-thiolato]-Ni(II),-Pd(II),and -Pt(II) Complexes,and Molecular Structure of the Ni(II) Complex" Bull.Chem.Soc.Jpm.65. 2272-2274 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki and J.Fujita: "A New Palladium(I) Dinuclear Complex Forming Coplanar Structure for Two Coordination Planes" Chem.Lett.1067-1068 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Ando,M.Kita,K.Kashiwabara,J.Fujita,S.Kurachi,and S.Ohba: "Preparation and Characterization of Co(III) Complexes Containing 1,1,1-Tris(dimethylphosphino)ethane(mmtp),and the Crystal Structure of [Co(mmtp)_2][Co(CN)_6]2.25H_2O" Bull.Chem.Soc.Jpn.65. 2748-2755 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,M.Okuno,K.Kashiwabara,and J.Fujita: "Preparation and Characterization of Co(III)-dtc Complexes Containing 1,2-Bis(dimethoxyphosphino)ethane.Molecular Structures of [Co(dtc)[R_2P(CH_2)_2PR_2]](BF_4)_2(R=CH_3O,CH_3)" Bull.Chem.Soc.Jpn.65. 3042-3048 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Matsui,M.Kiata,K.Kashiwabara,and J.Fujita: "Preparation and Characterization of dtc-Co(III) Complexes Containing Phosphites,and Molecular Structures of [Co(dtc)_2(etpb)_2]BF_4 and [Co(pipdtc)(pome)_4](BF_4)_2" Bull.Chem.Soc.Jpn.66. (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,K.Nemoto,K.Kashiwabara,J.Fujita,M.Goto,T.Miyamoto,and S.Ohba: "Molecular Structures of [Co(acac)_2[(CH_3)X CH_2 CH_2 NH_2]]ClO_4 (X=N,P,As;acac=2,4Pentanedionateion)" Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki and J.Fujita: "Preparation and Characterization of Palladium(I) and Platinum(I) Dinuclear Complexes Bridged by 2-(Dimethylphosphino)pyridine." Bull. Che. Soc. Jpn.65. 1016-1025 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki,N.Iitaka, S.Kurach, M.Kita, K.KAshiwabara, S.Ohba,and J.Fujita: "Molecular Structures of HT-[MM'Cl_2(Me_2Ppy)_2](MM'=Pd_2,PdPt,Pt_2;Me_2Ppy=2-(Dimethylphosphino)pyridine) and HT-[Pd_2Cl_2(Ph_2Ppy)_2](ph_2Ppy=2-(Diphenylphosphino)pyridine)." Bull. Che. Soc. Jpn.65. 1817-1824 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Adachi,M.Kita,K.Kashiwabara,J.Fujita,N.Iitaka,S.Kurachi,S.Ohba,and D.Jin: "Preparation and Characterization of Co(III) Complexes Containing dppf or dmpf as a Bidentate Ligand,and Molecular Structures of [Co(acac)_2(dmpf)]B(C_6H_5)_4, and[Co(dtc)_2(dmpf)]B(C_6H_5)_4." Bull. Chem. Soc. Jpn.65. 2037-2044 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,T.Yamamoto,K.Kashiwabara,and J.Fujita: "Bis{2-(dimethylphosphino)ethane-l-thiolato}-Ni(II), -Pd(II),and-Pt(II) Complexes, and Molecular Structure of the Nickel(II) Complex." Bull. Chem. Soc. Jpn.65. 2272-2274 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki and J.Fujita.: "A New Palladium(I) Dinuclear Complex Forming a Coplanar Structure for Two Coordination Planes." Chem. Lett.1067-1068 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Ando,M.Kita,K.Kashiwabara,J.Fujita,S.Kurachi, and S.Ohba.: "Preparation and Characterization of Co(III) Complexes Containing 1,1,1-Tris(dimethylphosphino)ethane (mmtp), and the Crystal Structure of [Co(mmtp)_2][Co(CN)_6]2.25H_2O." Bull. Chem. Soc. Jpn.65. 2748-2755 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,M.Okuno,K.Kashiwabara, and J.Fujita: "Preparation and Characterization of Co(III)-dtc Complexes Containing 1,2-Bis(dimethoxylphosphino)ethane. Molecular Structures of [Co(dtc){R_2P(CH_2)_2PR_2}_2](BF_4)(R=CH_3O, and CH_3)." Bull. Chem. Soc. Jpn.65. 3042-3048 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Matsui,M.Kita,K.Kashiwabara, and J.Fujita: "Preparation and Characterization of Dithiocarbamato-Co(III) Complexes Containing Phosphites, and Molecular Structures of cis-[Co(dtc)_2(etpb)_2]BF_4 and [Co(pipdtc)(pome)_4](BF_4)2_2." Bull. Chem. Soc. Jpn.66.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Kita,K.Nemoto,K.Kashiwabara,J.Fujita,M.Goto,T.Miyamoto, and S.Ohba.: "Molecular Structures of [Co(acac)_2{(CH_3)XCH_2CH_2NH_2}]ClO_4(X=N,P,As;acac=2,4Pentanedionate ion)." Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki and J.Fujita: "A New Palladium(I)Dinuclear Complex Forming a Coplanar Structure for Two Coordination Planes" Chem.Lett.1067-1068 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] T.Ando,M.Kita,K.Kashiwabara,J.Fujita,S.Kurachi,and S.Ohba: "Preparation and Characterization of Co(III)Complexes Containing 1,1,1-Tris(dimethylphosphino)ethane(mmtp),and the Crystal Structure of [Co(mmtp)_2〕[Co(CN)_6]2.25H_22O" Bull.Chem.Soc.Jpn.65. 2748-2755 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Kita,M.Okuno,K.Kashiwabara,and J.Fujita: "Preparation and Characterization of Co(III)-dtc Complexes Containing 1,2-Bis(dimethoxyphosphino)ethane. Molecular Structures of [Co(dtc){R_2P(CH_2)_2PR_2}_2](BF_4)_2(R=CH_3O,CH_3)" Bll.Chem.Soc.Jpn.65. 3042-3048 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Matsui,M.Kiata,K.Kashiwabara,and J.Fujita: "Preparation and Characterization of dtc-CO(III)Complexes Containing Phosphites,and Molecular Structures of [Co(dtc)_2(etpb)_2]BF_4and[Co(pipdtc)(pome)_4〕(BF_4)_2" Bull.Chem.Soc.Jpn.66. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Kita,K.Nemoto,K.Kashiwabara,J.Fujita,M.Goto,T.Miyamoto,and S.Ohba: "Molecular Structures of[Co(acac)_2{(CH_3)XCH_2CH_2NH_2}]CIO_4(X=N,P,As;acac=2,4-Pentanedionateion)" Bull.Chem.Soc.Jpn.

    • Related Report
      1992 Annual Research Report
  • [Publications] Takayoshi SUZUKI;Junnosuke FUJITA: "Preparation and Characterization of Palladium(I) and Platinum(I) Dinuclear Complexes Bridged by 2ー(Dimethylphoshino)pyridine" Bull.Chem.Soc.Jpn.No.4. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Takayoshi SUZUKI,Naoyuki IITAKA,Saeko KURACHI,Masakazu KITA,Kazuo KASHIWABARA,S.OHBA,Junnosuke FUJITA: "Molecular Structures of HTー[MM^IC]_2(μーMe_2Ppy)_2](MM^I=Pd_2,PdPt,and Pt_2;Me_2Ppy=2ー(dimethylphosphino)pyridine)and THー[Pd_2C]_2(μーPh_2Ppy)_2](Ph_2Ppy=2ー(diphenylphosphino)pyridine)" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report
  • [Publications] Masakazu KITA,Takashi YAMAMOTO,Kazuo KASHIWABARA,Junnosuke FUJITA: "Bis{2ー(dimethylphosphino)ethaneー1ーthiolato}ーnickel(II),ーpalladium(II),andーplatinum(II) Complexes,and Molecular Structure of the Ni Complex" Bull.Chem.Soc.Jan.

    • Related Report
      1991 Annual Research Report
  • [Publications] Masahiro ADACHI,Masakazu KITA,Kazuo KASHIWABARA,Junnosuke FUJITA,Naoyuki IITAKA,Saeko KURACHI,Shigeru OHBA,JIN DouーMan: "Preparation and Characterization of Co(III) Complexes Containing 1,1'ーBisー(diphenylphosphino)ferrocene(dppf) or 1,1'ーBis(dimethylphosphino)ーferrocene(dmpf) as a Bidentate Ligand,and Molecular Structures of [Co(acac)_2(dmpf)]B(C_6H_5)_4 and [Co(dtc)_2(dmpf)]B(C_6H_5)_4" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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