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2004 Fiscal Year Final Research Report Summary

Development of Structurally Constrained Metal Clusters Leading to Functional Nano-Molecular Devices

Research Project

Project/Area Number 13304053
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionNara Women's University

Principal Investigator

TANASE Tomoaki  Nara Women's University, Faculty of Science, Professor, 理学部, 教授 (50207156)

Co-Investigator(Kenkyū-buntansha) AOSHIMA Takayuki  Mitsubishi Chemical Group, Research Center, Senior Researcher, 横浜総合研究所, 副主任研究員
Project Period (FY) 2001 – 2004
KeywordsMetal Cluster / Metal-metal Bond / Hexanuclear Complex / Platinum / Tridentate Phosphine / Bisisocyanide / Quantum Wire / Nano-structured Molecule
Research Abstract

Linear transition-metal clusters have recently attracted increasing attention concerning their unique structural, optical, and electrochemical properties. Attempts to build up much expanded molecules with multi-functional metal-metal interactions are highly desired in relation to development of molecular-based electronic devices as well as to exploration of unprecedented physical and chemical behaviors. In this project, we have studied the syntheses, characterization, and reactivities of linear hexanuclear clusters. Reduction of Pt_3 complex 1 with NaBH_4 in E_tOH afforded the linear hexaplatinum cluster, [Pt_6(μ-H)(μ-dpmp)_4(RNC)_2(PF_6)_3 (3), whereas the analogous heterometallic cluster, [Pt_4Pd_2(μ-H)(μ-dpmp)_4(RNC)_2](PF_6)_3 (4), was synthesized from reaction of Pt_2Pd complex 2 with NaOMe ([PL_2M(μ-dpmp)_2(RNC)_2](PF_6)_2 (M=Pt (1), Pd (2); dpmp=bis(diphenyl- phosphinomethyl)phenylphosphine, RNC=organoisocyanide). Complex 3a (R=Xyl) is a trivalent, 86e-cluster and involves a linear Pt_6 core (Pt-Pt(central)=3.3092(5) Å, Pt-Pt(inner)=av. 2.733 Å, Pt-Pt(outer)= av. 2.704 Å) supported by four dpmp ligands and terminally coordinated by two isonitriles. The clusters 3a and 4a readily underwent two-electron oxidation to afford [Pt_4Pd_2(μ-dpmp)_4(RNC)_2](PP_6)_4 (M=Pt (5a), Pd (5b)). Reduction of 1 with NaBH_4 in DMF afforded dark green trihydride hexaplatinum complex, [Pt_6(μ-H)(H)_2(μ-dpmp)_4](PF_6) which was interestingly converted into neutral hexplatinum cluster with coordinatively unsaturated terminals, [Pt_6(μ-H)_2(μ-dpmp)_4] (6). The trihydride cluster readily reacted with Mel to give [Pt_6(μ-H)(I)_2(μ-dpmp)_4](PF_6). These linear clusters with hydrides could be of significant importance as reactive functional metal wires coupled with redox processes. The SAM's (self assembled monolayer) of bisisocyanide-linked 3a were prepared and characterized by electrochemical methods.

  • Research Products

    (35 results)

All 2005 2004 2002 2001

All Journal Article (33 results) Book (2 results)

  • [Journal Article] Tetranuclear Copper(II) Complex with Glucose-1-phosphate and Its Phosphate Ester Exchange with ATP2005

    • Author(s)
      M.Kato, T.Tanase
    • Journal Title

      Inorg. Chem. (American Chemical Society) 44

      Pages: 8-10

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Trinuclear Cu(II) Complex of 4,6-O-Ethylidene-β-D-glucopyranosylamine Derived Schiff Base Ligand and Its Reactivity Towards Primary Alcohols and Amines2005

    • Author(s)
      A.K.Sah, M.Kato, T.Tanase
    • Journal Title

      Chem. Commun. (Royal Society of Chemistry)

      Pages: 675-677

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cage-type Hexanuclear Platinum(0) Clusters with Diphosphine and Isocyanide Ligands Encapsulatine Two Mercury(0) Atoms2005

    • Author(s)
      T.Tanase, E.Goto et al.
    • Journal Title

      Organometallics (American Chemical Society) 24

      Pages: 234-244

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Tetranuclear Copper(II) Complex with Glucose-1-phosphate and Its Phosphate Ester Exchange with ATP2005

    • Author(s)
      M.Kato, T.Tanase
    • Journal Title

      Inorg.Chem.(American Chemical Society) 44

      Pages: 8-10

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Trinuclear Cu(II) Complex of 4,6-O-Ethylidene-β-D-glucopyranosylamine Derived Schiff Base Ligand and Its Reactivity Towards Primary Alcohols and Amines2005

    • Author(s)
      A.K.Sah, M.Kato, T.Tanase
    • Journal Title

      Chem.Commun.(Royal Society of Chemistry)

      Pages: 675-677

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cage-type Hexanuclear Platinum(0) Clusters with diphosphine and Isocyanide Ligands Encapsulating Two Mercury(0) Atoms2005

    • Author(s)
      T.Tanase, E.Goto et al.
    • Journal Title

      Organometallics (American Chemical Society) 24

      Pages: 234-244

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Crystal Structure and Mesomorphism Appeard in Oxovanadium(IV) Salen Complexes with 4-Substituted Long Alkoxy Chains2004

    • Author(s)
      Y.Abe, T.Tanase et al.
    • Journal Title

      Inorg. Chem. Commun. (Elsevier) 7

      Pages: 580-583

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Reactive Rigid-Rod Organometallic Polymers Involving Linear Triplatinum Units Connected by π-Conjugated Bisisocyanide2004

    • Author(s)
      T.Tanase, E.Goto et al.
    • Journal Title

      Organometallics (American Chemical Society) 23

      Pages: 5975-5988

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Linear Redox-Active Pt_6 and Pt_2Pd_2Pt_2 Clusters2004

    • Author(s)
      E.Goto, T.Tanase et al.
    • Journal Title

      Angew. Chem. Int. Ed. (Wiley-VCH) 43

      Pages: 5029-5032

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Electron-Rich Diplatinum(0) Metallocryptate Promoting Novel Successive Encapsulation of Acidic Hydrides2004

    • Author(s)
      E.Goto, T.Tanase et al.
    • Journal Title

      Organometallics (American Chemical Society) 23

      Pages: 6042-6051

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Fromation of Thermotropic and Lyotropic Liquid Crystals of Bis(N-alkylethylenediamine)silver(I) Nitrate2004

    • Author(s)
      M.Iida, T.Tanase et al.
    • Journal Title

      Eur. J. Inorg. Chem. (Wiley-VCH)

      Pages: 3920-3929

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Novel Crystal Structure and Mesomorphism Appeared in Oxovanadium(IV) Salen Complexes with 4-Substituted Long Alkoxy Chains2004

    • Author(s)
      Y.Abe, T.Tanase et al.
    • Journal Title

      Inorg.Chem.Commun.(Elsevier) 7

      Pages: 580-583

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reactive Rigid-Rod Organometallic Polymers Involving Linear Triplatinum Units Connected by π-Conjugated bisisocyanide2004

    • Author(s)
      T.Tanase, E.Goto et al.
    • Journal Title

      Organometallics (American Chemical Society) 23

      Pages: 5975-5988

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Linear Redox-Active Pt_6 and Pt_2Pd_2Pt_2 Clusters2004

    • Author(s)
      E.Goto, T.Tanase et al.
    • Journal Title

      Angew.Chem.Int.Ed.(Wiley-VCH) 43

      Pages: 5029-5032

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Formation of Thermotropic and Lyotropic Liquid Crystals of Bis(N-alkylethylenediamine)silver(I) Nitrate2004

    • Author(s)
      M.Iida, T.Tanase et al.
    • Journal Title

      Eur.J.Inorg.Chem.(Wiley-VCH)

      Pages: 3920-3929

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Recent Development of Linearly Ordered Multinuclear Transition-Metal Comnlexes (Accounts)2002

    • Author(s)
      T.Tanase
    • Journal Title

      Bull. Chem. Soc. Jpn. (Chemical Society of Japan) 75

      Pages: 1407-1422

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Recent Development of Linearly Ordered Multinuclear Transition-Metal Complexes (Accounts)2002

    • Author(s)
      T.Tanase
    • Journal Title

      Bull.Chem.Soc.Jpn.(Chemical Society of Japan) 75

      Pages: 1407-1422

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Unsymmetrical A-Frame Pt_2Pd Trinuclear Complexes : Site-Selective Apparent Double Insertion of Alkynes into Pd-Pt and Pd-P Bonds2001

    • Author(s)
      T.Tanase, R.A.Begum
    • Journal Title

      Organometallics (American Chemical Society) 20

      Pages: 106-114

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Linearly Ordered Pt_2Rh and Pt_2Ir Heterotrinuclear Complexes Bridged by Tridentate Phosphine Ligands2001

    • Author(s)
      T.Tanase, R.A.Begum, H.Toda et al.
    • Journal Title

      Organometallics (American Chemical Society) 20

      Pages: 968-979

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Insertion of Strongly Electron Withdrawing Cyanoolefins into the C-H Bond in Pentamethyl-cyclo pentadienyl-Rhodium(III) and -Iridium(III) Complexes Containing P-O or P-O-O' Coordinations2001

    • Author(s)
      Y.Yamamoto, T.Tanase et al.
    • Journal Title

      Organometallics (American Chemical Society) 20

      Pages: 266-272

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cyclic Dimerization of Tetracyanoethylene Promoted on Linear Triplatinum Centres Leading to Novel Nitrene-Bridged Pt_3 Complexes2001

    • Author(s)
      T.Tanase, M.Hamaguchi et al.
    • Journal Title

      Chem. Commun. (Royal Society of Chemistry)

      Pages: 1072-1073

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Trinuclear Zn(II) and Cu(II) Homo- and Heterotrimetallic Complexes Involving D-Glucopyranosyl and Biscarboxylate Bridging Ligands. A Substrate Binding Model of Xylose Isomerases2001

    • Author(s)
      T.Tanase, H.Inukai et al.
    • Journal Title

      Inorg. Chem. (American Chemical Society) 40

      Pages: 3943-3953

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Diruthenium Complexes with Hydrotris(1-pyrazolyl)borate Face-Capping Ligands Involving {Ru_2(μ-O or μ-OH)(μ-carboxylato)_2} Cores2001

    • Author(s)
      T.Tanase, N.Takeshita et al.
    • Journal Title

      J. Chem. Soc., Dalton Trans. (Royal Society of Chemistry)

      Pages: 2293-2302

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation and Characterization of Palladium and Platinum Complexes Bearing 1,8-Bis[(diphenylphosphino)methyl]naphthalene2001

    • Author(s)
      Y.Yamamoto, T.Tanase et al.
    • Journal Title

      J. Chem. Soc., Dalton Trans. (Royal Society of Chemistry)

      Pages: 1773-1781

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Substrate-dependent Chemoselective Aldose-Aldose and Aldose-Ketose Isomerizations of Carbohydrates Promoted by a Combination of Calcium Ion and Monoamines2001

    • Author(s)
      T.Tanase, T.Takei et al.
    • Journal Title

      Carbohydr. Res. (Elsevier) 333

      Pages: 303-312

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Sugar-Pendant Diamines2001

    • Author(s)
      Y.Mikata, T.Tanase et al.
    • Journal Title

      J. Org. Chem. (American Chemical Society) 66

      Pages: 3783-3789

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Insertion of Strongly Electron Withdrawing Cyanoolefins into the C-H Bond in Pentamethyl-cyclopentadienyl-Rhodium(III) and -Iridium(III) Complexes Containing P-O or P-O-O' Coordinations2001

    • Author(s)
      Y.Yamamoto, T.Tanase et al.
    • Journal Title

      Organometallics (American Chemical Society) 20

      Pages: 266-272

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cyclic Dimerization of Tetracyanoethylene Promoted on Linear Triplatinum Centers Leading to Novel Nitrene-Bridged Pt_3 Complexes2001

    • Author(s)
      T.Tanase, M.Hamaguchi et al.
    • Journal Title

      Chem.Commun.(Royal Society of Chemistry)

      Pages: 1072-1073

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Trinuclear Zn(II) and Cu(II) Homo- and Heterotrimetallic Complexes Involving D-Glucopyranosyl and Biscarboxylate Bridging Ligands. A Substrate Binding Model of Xylose Isomerases2001

    • Author(s)
      T.Tanase, H.Inukai et al.
    • Journal Title

      Inorg.Chem.(American Chemical Society) 40

      Pages: 3943-3953

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Diruthenium Complexes with Hydrotris(1-pyrazoly)borate Face-Capping Ligands Involving {Ru_2(μ-O or μ-OH)(μ-carboxylato)_2} Cores2001

    • Author(s)
      T.Tanase, N.Takeshita et al.
    • Journal Title

      J.Chem.Soc., Dalton Trans.(Royal Society of Chemistry)

      Pages: 2293-2302

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation and Characterization of Palladium and Platinum Complexes Bearing 1,8-Bis[(diphenylphosphino)methyl]naphthalene2001

    • Author(s)
      Y.Yamamoto, T.Tanase et al.
    • Journal Title

      J.Chem.Soc., Dalton Trans.(Royal Society of Chemistry)

      Pages: 1773-1781

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Substrate-dependent Chemoselective Aldose-Aldose and Aldose-Ketose Isomerizations of Carbohydrates Promoted by a Combination of Calcium Ion and Monoamines2001

    • Author(s)
      T.Tanase, T.Takei et al.
    • Journal Title

      Carbohydr.Res.(Elsevier) 333

      Pages: 303-312

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Sugar-Pendant Diamines2001

    • Author(s)
      Y.Mikata, T.Tanase et al.
    • Journal Title

      J.Org.Chem.(American Chemical Society) 66

      Pages: 3783-3789

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] 実験化学講座22 金属錯体・遷移金属クラスター2004

    • Author(s)
      日本化学会編(分担執筆)
    • Total Pages
      538
    • Publisher
      丸善株式会社
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] The 5th Series of Experimental Chemistry No 22 Metal Complexes & Transition Metal Clusters2004

    • Author(s)
      Chemical Society of Japan (incl.T.Tanase)
    • Total Pages
      538
    • Publisher
      Maruzen Co.Inc.
    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2007-12-13  

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