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Characteristic Reactivties and Functions of Metal Complexes containing Hypodentate Ligands.

Research Project

Project/Area Number 12440183
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionHOKKAIDO UNIVERSITY

Principal Investigator

SASAKI Yoichi  Hokkaido Univ., Grad. School of Sci., Prof., 大学院・理学研究科, 教授 (30004500)

Co-Investigator(Kenkyū-buntansha) TSUGE Kiyosi  Hokkaido Univ., Grad. School of Sci., Inst., 大学院・理学研究科, 助手 (60280583)
ABE Masaaki  Hokkaido Univ., Grad, School of Sci., Inst., 大学院・理学研究科, 助手 (90260033)
Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2001: ¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 2000: ¥9,800,000 (Direct Cost: ¥9,800,000)
KeywordsHypodentate Ligands / Transition Metal Coplexes / Photoluminescence / X-Ray Structural Analysis / Dynamic Exchange / Redox Reactions / Heavy Transition Elements / Platinum Complexes / レニウム錯体 / ルテニウム錯体 / 発光スペクトル / レニウムカルボニル錯体 / オキソバナジウム錯体
Research Abstract

Hypodentate ligand is defined as a ligand in which fewer than the maximum possible number of donor atoms are bonded to metal centers. The purpose of the study is to prepare various new complexes containing such ligands and to investigate their reactivities and functional characteristics. In particular we have paid special attention to luminecent complexes as the control of photophysical properties by using uncoordinated ligand moieties are promising. The results obtained by using polypyridyl ligands such as tris(2-pyridylmethyl)amine (tpa) and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) are as follows, (i) A series of planar Pt(II) and Pd(II) complexes with these ligands all have uncoordinated arms. The exchange of the free and coordinated arms have been found in the order Pt(II) < Pd(II) and tpa < tpen. (ii) Luminescent [Re(CO)_3(tpa)]^+ has been prepared which also has one uncoordinated arm that does not undergo exchange with the coordinated ones. (iii) V^<IV>O complexes of tpa has fully coordinated tpa (tetradentate), different from ReO-tpa complexes which have tridentate tpa, but with tpen V^<IV>O complex containing hypodentate ligand has been isolated. With the diphosphine ligands Ph_2P(CH_2)_nPPh_2 (n = 1 - 5), a series of luminescent hexarhenium cluster complexes containing monodentate diphosphines have been obtained. For the hexarhenium unit, we have also successfully introduced giant ligands free base pyridylporphyrines. We have also used a small polydentate ligand, 2.5-dimercapto-1,3,4-thiadiazole(McMTH). The complexes prepared include those containing a monodentate McMT are [Pt(terpy) (McMT)]^+ and [Ru(terpy)(bpy)(McMT)]^+. They react with another Pt(terpy)-unit to form homo and hetero dinuclear complexes. Furthermore various type of Cu(I) and Ag(I) complexes of McMT ligands have been obtained. All these McMT complexes are strongly luminescent.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Zhong-Ning Chen: "Octa(μ_3-selenido)hexarhenium(III)Cluster Complexes Containing Axial Diphosphine or Diphosphine Monooxide Ligands"Chemistry, A Europian Journal. 7巻. 4447-4455 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hideki Sugimoto: "Comparative Structural, Spectrophotometric and Redox Studies of Isostructural Complexes of Ruthenium(III), Osmium(III), and Rhenium(III) : cis-Dichloro Complexes Containing Tris(2-pyridylmethyl)amine and Its 6-Methylpyridyl Derivative"Bulletin of the Chemical Society of Japan. 74(11). 2091-2099 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Akira Sato: "Cyclic Voltammetric Observation of CO/aqua Terminal Ligand Substitution Reactions for Trinuclear Ruthenium Complexes at Self-Assembled Monolayer Interfaces"Physical Chemistry, Chemical Physics. 3(16). 3420-3426 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Zhong-Ning Chen: "Chelate Formation around the Hexarhenium Cluster Center by a Diphosphane Ligand, Ph_2P(CH_2)_6PPh_2"Angewandte Chemic, International Edition. 40(1). 178-179 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Tetsuaki Fujihara: "Synthesis, Properties and Crystal Structure of a Novel Anthracene-Bridged Mo-Zn Porphyrin Dimer"Inorganic Chemistry. 41(5). 1170-1176 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Ai Itasaka: "Octahedral Arrangement of Porphyrin Moieties around the Hexarhenium(III) Cluster Core. Crystal Structire of (μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-tritolyl-porphyrin)hexarhenium(III)(2+)"Angewandte Chemic, International Edition. 41(No.4). 463-466 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Zhong-Ning Chen, et al.: "Octa(μ_3-selenido)hexarhenium(III) Cluster Complexes Containing Axial Diphosphine or Diphosphinemonoxide Ligands.Chelate"Chemistry, A Europian Journal. 7(No.20). 4447-4455 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hideki Sugimoto, et al.: "Comparative Structural, Spectrophotometric and Redox Studies of Isostructural Complexes of Ruthenium(III), Osmium(III), and Rhenium(III) : cis-Dichloro"Bulletin of the Chemical Society of Japan. 74(No.11). 2091-2099 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Akira Sato, et al.: "Cyclic Voltammetric Observation of CO/aqua Terminal Ligand Substitution Reactions for Trinuclear Ruthenium Complexes at Self-Assembled Monolayer Interfaces"Physical Chemistry Chemical Physics. 3(No.16). 3420-3426 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Zhong-Ning Chen, et al.: "Chelate Formation around the Hexarhenium Cluster Center by a Diphosphane Ligand, Ph_2P(CH_2)_6PPh_2"Angewandte Chemie, International Edition. 40(No.1). 178-179 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Tetsuaki Fujihara, et al.: "Synthesis, Properties and Crystal Structure of a Novel Anthracen e-Bridged Mo-Zn Porphyrin Dimer"Inorganic Chemistry. 41(No.5). 1170-1176 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Ai Itasaka, et al.: "Octahedral Arrangement of Porphyrin Moieties around the Hexarhenkium(III) Cluster Core. Crystal Structure of (μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-trirolylporphyrin)hexarheniurn(III) (2+)"Angewandte Chemie, International Edition. 41(No.4). 463-466 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Ai Itasaka: "Octahedral Arrangement of Porphyrin Moieties around the Hexarhenium(III) Cluster Core. Crystal Structire of (μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-tritolylporphyrin)hexarhenium(III)(2+)"Angewandte Chemie,International Edition. 41(No.4). 463-466 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Zhong-Ning Chen: "Octa(μ_3-selenido)hexarhenium(III) Cluster Complexes Containing Axial Diphosphine or Diphosphine Monooxide Ligands"Chemisry,A Europian Journal. 7巻. 4447-4455 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hideki Sugimoto: "Comparative Structural, Spectrophotometric and Redox Studies of Isostructural Complexes of Ruthenium(III), Osmium(III), and Rhenium(III): cis-Dichloro Complexes Containing Tris(2-pyridylmethyl)amine and Its 6-Methylpyridyl Derivative"Bulletin of the Chemical Society of Japan. 74(11). 2091-2099 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Akira Sato: "Cyclic Voltammetric Observation of CO/aqua Terminal Ligand Substitution Reactions for Trinuclear Ruthenium Complexes at Self-Assembled Monolayer Interfaces"Physical Chemistry Chemical Physics. 3(16). 3420-3426 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masaaki Abe: "A Kinetic Study on Pyridine Exchange Reactions at a Bis(μ-acetato)(μ-oxo)diruthenium(III) Center: Effects of Monodentate and Bidentate N-Heterocyclic Ligands cis to the Oxo Bridge"Inorganica Chimica Acta. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tetsuaki Fujihara: "Synthesis, Properties and Crystal Structure of a Novel Anthracene-Bridged Mo-Zn Porphyrin Dimer"Inorganic Chemistry. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Zhong-Ning Chen: "Chelate Formation around the Hexarhenium Cluster Center by a Diphosphane Ligand, Ph_2P(CH_2)_6PPh_2."Angewandte Chemie, International Edition in English. 40(No.1). 239-242 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Maxim Sokolov: "Synthesis and Crystal Structure of [Ru_2 (μ-pyS)_3 (pyS)_2](CF_3SO_3) : the First Ru (III) Complex of 2-Mercaptopyridine. "Inorganic Chemistry Communications. 4巻(印刷中). (2001)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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