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Syntheses of Transition Metal-Sulfur Clusters and Development of Their Novel Functions

Research Project

Project/Area Number 62470083
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

HIDAI Masanobu  Fac. of Eng., Univ. of Tokyo; Professor, 工学部, 教授 (60011011)

Co-Investigator(Kenkyū-buntansha) MIZOBE Yasushi  Fac. of Eng., Univ. of Tokyo; Research Associate, 工学部, 助手 (40175609)
YANO Shigenobu  Fac. of Sci., Nara Women's Univ.; Professor, 理学部, 教授 (60011186)
Project Period (FY) 1987 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1989: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1988: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1987: ¥4,000,000 (Direct Cost: ¥4,000,000)
KeywordsTransition-metal / Cluster / Thiolate / Sulfide / Ruthenium / Palladium / Molybdenum / Electroconductivity / 金属-硫黄ポリマ- / ルテニウム-硫黄クラスター / 混合金属-硫黄クラスター / ルテニウム-チオラート二核錯体 / ルテニウムー硫黄クラスター・ / パラジウムーモリブデンー硫黄クラスター / 電導性
Research Abstract

1. A series of diruthenium complexes with two or three bridging thiolate ligands, [Cp^*Ru(K-SR)_3RuCp^*]C1, [Cp^*RuC1(mu-SR)_2RuCp^*C1], [Cp^*Ru(mu-SR)_3RuCp^*], and [Cp^*Ru(mu-S-i-Pr)_2RuCp^*] Were prepared by treatment of [Cp^*RuC1_2]_2 with various thiolate compounds (Cp^* = eta^5-C_5Me_5), the structures of which were determined by the X-ray analyses or the EXAFS study. The products sharply depended upon the nature of the thiolate compounds and reaction conditions. The reactions of these complexes with CO, t-BuNC, and H_2 were also undertaken and several novel diruthenium complexes with CO, t-BuNC, and hydride ligands, [Cp^*RuCl(mu-SR)_2RuCp^*(L)]C1, [Cp^*Ru(SR)(mu-SR)_2RuCp^*(L)], [Cp^*Ru(mu-CO)( mu-SR)_2RuCp^*] and [Cp^*RuH(mu-SR)_2RuCp^*H] (L = CO, t-BuNC) were isolated and characterized.
2. The Mo-sulfido cluster [Mo_3S_4(H_2O)_9]^<4+> reacted with Pd powder in diluted hydrochloric acid for several days to give a novel Pd-Mo-sulfido cluster [Pd_2Mo_6S_8(H_2O)_<18>]^<8+>. The double cubane structure with the bridging Pd-S bonds between two PdMo_3S_4 cores was demonstrated by the X-ray analysis. Treatment of the blue solution of this cluster in methanol with olefins such as ethylene and 1,5-cyclooctadiene resulted in the rapid color change to red, whereas analogous treatment with acetylenes such as PhC2 XI CPh and 2-butyne also afforded red solutions but much more slowly. ^1H NMR study in methanol-d_4 disclosed the coordination of ethylene presumably at the Pd site in this cluster.
3. Polymeric transition metal-sulfur compounds including [Fe_4S_4]^<2+> or [Cp^*_22Ru_2]^<4+> cores linked by m- or p-benzenedithiolate ligands were prepared by the reactions of [Fe_4S_4(S-t-Bu)_4]^<2-> or [Cp^*RuC1_2]_2 with corresponding benzenedithiols. The disks prepared from these compounds-in'solid form showed the electroconductivities included in the range of those for semiconductors.

Report

(4 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • 1987 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] TANASE,TOMOAKI: "An EXAFS Study of Binuclear Ruthenium(III)Complexes with Two and Three Bridging Thiolate Ligands" New J.Chem.12. 697-698 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] DEV,SOMANATH: "Preparation,Properties and Some Reactions of Novel Ruthenium Thiolate Complexes" Organometallics. 8. 1232-1237 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] DEV,SOMANATH: "Synthesis and Reactions of Diruthenium Thiolate Complexes[Cp^*Ru(μ-SR)_3RuCp^*](Cp^*=η^5-C_5Me_5;R=i-Pr,Et,Cy,Bn,Ph)" Organometallics(submitted).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] TANASE, TOMOAKI; et al.: "An EXAFS Study of Binuclear Ruthenium(III) Complexes with Two and Three Bridging Thiolate Ligands" New J. Chem., 12, 697-698, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] DEV, SOMANATH; et al.: "Preparation, Properties and Some Reactions of Novel Ruthenium Thiolate Complexes" Organometallics, 8, 1232-1237, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] DEV, SOMANATH; et al.: "Synthesis and Reactions of Diruthenium Thiolate Complexes [Cp^*Ru(mu-SR)_3RuCp^*] (Cp^*=7^5-C_5Me_5; R=i-Pr, Et, cyclohexyl, benzyl, Ph)" Organometallics.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Somanath Dev: "Preparation,Properties and Some Reactions of Novel Ruthenium Thiolate Complexes" Organometallics. 8. 1232-1237 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Somanath Dev: "Synthesis and Reactions of Diruthenium Thiolate Complexes [Cp^※Ru(μ-SR)_3RuCp^※](Cp^※=η^5-C_5Me_5;R=i-Pr,Et,cyclohexyl,Ph)" Organometallics.

    • Related Report
      1989 Annual Research Report
  • [Publications] Tomoaki;Tanase: New J.Chem.12. 697-698 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Somanath;Dev: Organometallics. (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Tanase;K.Imogawa;S.Dev;Y.Mizobe;S.Yano;M.Hidai: New J.Chem.(1988)

    • Related Report
      1987 Annual Research Report

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

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