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Synthesis of Platinum group metal cluster complexes with redox active ligands.

Research Project

Project/Area Number 08640704
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionHokkaido University

Principal Investigator

UMAKOSHI Keisuke  Hokkaido Univ., Graduate School of Sci., Research associate, 大学院・理学研究科, 助手 (20213481)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1997: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1996: ¥1,300,000 (Direct Cost: ¥1,300,000)
Keywordsplatinum / rhenium / pyridinethiol / polysulfide / sulfur / inter-element / polynunclear complex / reaction mechanism / クラスター錯体 / テトラスルフィド / 金属硫化物イオン / タングステン
Research Abstract

The commercial hydrodesulfurization (HDS) catalysts generally comprise metal sulfides supported on gamma-alumina. Molybdenum or tungsten are essential components but the catalytic activity increases remarkably by addition of other transition metals such as Ni, Co, Ru, Ir, Rh, Pt, Pd, Os, Re as promoters. The role playd by these promoters is still unknown. Although the isolation and characterization of the intermediate species that is formed prior to the desulfurization step are attracting much attention, such model complexes are still far from the structure of the surface of the catalysts. It is very important to study and understand the reaction of thiometallate anions with metal complexes which can be promoters.
In the course of our study of the reaction of dinuclear Pt (III) complexes of pyridinethiol, [Pt_2Cl_2(5-mpyt)_4] , With tetrathiotungstate, WS_4^<2->, we unexpectedly found the formation of tetrasulfido bridged dimer of the "Pt_2" unit, [{ ClPt_2(5-mpyt)_4}_2S_4]. The formation of tetrasulfide anion (S_4^<2->) from tetrathiotungstate is very unusual, since we know only one example in which tetrathiometallate anions act as a source of disulfide anion (S_2^<2->). [{ClPt_2(5-mpyt)_4}_2S_4] Can be converted to the starting compound, [Pt_2Cl_2(5-mpyt)_4] , by exposing the CHCl_3 solution toward room light. The isolation of this compound enabled us to know whole the reaction in which WS_4^<2-> was converted to elemental sulfur via S_4^<2-> ion. The isolation of [(ClPt_2(5-mpyt)_4)_2S_4] corresponds to the identification of the intermediate compound of this reaction.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] K., Umakoshi: "Formation of a Novel μ-Tetrasulfido-Bridged Dimer of a Dinnclear Platinum Complex" Inorg.Chem. 36. 4296-4297 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.M.Botha: "Chelation Processes to an Oxorhenium(V) Center by N,N,N,O-Tetradeutate and N,N,O-Tridentate Ligands as Verified by structural and Mechanistic Studies of Intermediate Species" Iuorg.Chem. 37(in press). (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Keisuke Umakoshi: ""Formation of a Novel mu-Tetrasulfido Bridged Dimer of Dinuclear Platinum Complex"" Inorg.Chem.36. 4296-4297 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.Mattheus Botha: ""Chelation Processes to an Oxorhenium (V) Center by N,N,N,O-Tetradentate and N,N,O-Tridentate Ligands as Verified by Structural and Mechanistic Studies of Intermediate Species"" Inorg.Chem.37 (in press). (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Umakoshi: "Formation of a Novel u-Tetrasulfido-Bridged Dimer of a Dinnclear Platinum Complex" Inorg.Chem. 36・20. 4296-4297 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] J.M.Botha: "Chelation Processes to an Oxorhenium (V) Center by N,N,N,O-Tetradentate and N,N,O-Tridentate Ligands As Verified by Structural and Mechanistic Studies of Intermediate Species." Inorg.Chem. 37(in press). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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