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Isomerism of Dinuclear Platinum(II) Complex

Research Project

Project/Area Number 62470042
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 InstitutionFaculty of Science, Osaka City University

Principal Investigator

OOI Shun'ichiro  Faculty of Science, Osaka City University, 理学部, 教授 (00046913)

Co-Investigator(Kenkyū-buntansha) KINOSHITA Isamu  Faculty of Science, Osaka City University, 理学部, 助手 (80128735)
MATSUMOTO Keiji  Faculty of Science, Osaka City University, 理学部, 助教授 (50047164)
Project Period (FY) 1987 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥4,400,000 (Direct Cost: ¥4,400,000)
KeywordsPlatinum Complex / Dinuclear Pt(II) and (III) Complexes / Isomerism / 多核錯体 / 二核白金(II)、(III)錯体 / 二核白金(II)錯体 / 二核白金(III)錯体 / 異性現象
Research Abstract

Dunuclear Pt(II) pr (III) complex, having Pt(N-S)_4Pt core where the N-S represents a substituted pyridine-2-thiolato ligand (Rpyt), exists in four isomers. They are tentatively denoted as cis^-, trans^-, 3S- and 4S-isomers in which the former two have cis-PtS_2N_2 halves while the latter two invole PtS_3N and PtS_4 moieties. Lsolation and characterization have been made for the following 23 complexes: cis^- and trans^-[Pt_2(4-mpyt)_4], cis-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN), trans-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN), 3S-[Pt_2X_2(4-mpyt)_4](X=CI,Br,I,CN),cis-[Pt_2(CN)X(4-mpyt)_4](X=CI,Br,I,N_3), trans-[Pt_2(CN)X(4-mpyt)_4](X=CI,Br,I), 3S-[CN(N_3),I(S_3)]-[Pt_2(CN)I(4-mpyt)_4], 3S-[CN(S_3),I(N_3)]-[Pt_2(CN)I(4-mpyt)_4]. Collection has been made on the^<195>Pr and ^<13>C nmr data of these complexes. The ^<195>Pt chemical shifts are unable to explain in terms of the oxidation state of Pt, donor-atom property and energy separation of ground-excited state giving nonzero magnetic transition moment, indicating strong effect of Pt^<III>--Pt^<III> bonding. Kinetic parameters for cis-[Pt_2X_2(pyt)_4] + CN^--- cis-[Pt_2(CN)X(pyt)_4] + X^-, cis-[Pt_2(CN)X(pyt)_4] + Y^--- cis-[Pt_2(CN)Y(pyt)_4] + X^-, indicate the dissociative mechanism for these substitution reactions. The study for cis-[Pd_2(pyt)_4] dis- closed that the Pd^6+_ dimer is much less stable than the Pt^6+_ counterpart though the former is produced by electrochemical oxidation of the Pd^4+_ complex inpresence of halide ion.

Report

(3 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] Yasuno Yodota: Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yasuno,Yokota; Keisuke,Umakoshi; Isamu,Kinoshita; Shun'ichiro,Ooi: "Preparation and Substitution Reaction of Cyanohalotetrakis( -pyridine-2-thiolato)diplatinum(III)" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Isamu,Kinoshita; Keisuke,Umakoshi; Keiji,Matsumot; Shun'ichiro,Ooi: "Isomerism in Dinuclear Platinum (II) and (III) Complexes of 4-Methylpyridine-2-thiol"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Keisuke,Umakoshi; Akio,Ichimura; Isamu,Kinoshita; Shun'ichiro,Ooi: "Dinuclear Palladium Complex of Pyridine-2-thiol. Synthesis, Structure and Attempt to Oxidize It to Palladium (III) Dimer"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yasuno Yokota.: Bull.Chem.Soc.Jpn.

    • Related Report
      1988 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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