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Synthesis and Molecular Design of Novel Modified-Heteropolyanions Containing Multicenter Active Sites

Research Project

Project/Area Number 10640552
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

NOMIYA Kenji  Kanagawa University, Faculty of Science, Professor, 理学部, 教授 (80119354)

Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1999: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1998: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsModified Polyoxometalates / Dawson-type / Keggin-type / Vanadium (V)-substituted / Titanium (IV)-substituted / Catalysis / Toluene oxidation / Supported-organometallic complex / 修飾へテロポリ酸塩 / タングストポリ酸塩 / Cp^*RH^<2+> 基 / ベンゼン酸化 / 触媒前駆体 / 金属置換 / ニオブ(V) / チタン(IV) / バナジウム(V) / タングステン(VI)
Research Abstract

Several novel results in this research were obtained :
1. The Cp^*Rh^<2+> complex (Cp^* = C_5Me_5) supported on the V_3 surface (B-site) of 1, 4, 9-tri-vanadium(V)-substituted Keggin polyoxotungstate [1, 4, 9-PW_9V_3O_<40>]^<6-> was synthesized. The product also contained [Cp^*Rh(DMSO)_3]^<2+> as counterion.
2.Tri-Ti^<IV>-and di-Ti^<IV>-substituted Keggin polyoxotungstate were isolated as potassium salts and their X-ray crystal structures determined. Ultracentrifugation molecular weight (MW) measurements were also performed in aqueous solution. The two Ti^<IV>-substituted compounds in the solid state were dimeric, Ti-O-Ti anhydride forms of two α-Keggin [1, 2, 3-PW_9Ti_3O_<40>]^<9-> units and of two novel α-Keggin [1, 2-PW_<10>Ti_2O_<40>]^<7-> units, respectively. Solution MW measurements showed that the former was a dimer in pH7.0 aqueous solution, whereas the latter was a monomer in pH 7.8 aqueous solution.
3. The supported-polyoxotungstates formed between tri-metal-substituted Dawson polyoxotungstate [P_2W_<15>M_3O_<62>]^<9-> (M = Nb^V, V^V) and organometallic groups ((cod)Pt^<2+> and Cp^*Rh^<2+>) were synthesized, and the effects polyoxoanion-support (Nb vs. V) and organometallic species ((cod)Pt^<2+> vs. Cp^*Rh^<2+>) were elucidated.
4. Oxidation products of toluene and nitrobenzene with 30% aqueous H_2O_2 catalyzed by several vanadium(V)-substituted Keggin and Dawson polyoxometalates were carefully analyzed by GC/MS measurements. Polyoxometalates which promote the reaction via an ionic mechanism and via a radical mechanism were classified.

Report

(4 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] K.Nomiya et al.: "Synthesis of Triniobium(V)-Substituted SiW_9Nb_3O_<40>^<7-> Heteropolyoxoanions"Bull.Chem.Soc.Jpn.. 71(11). 2603-2610 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya and T.Hasegawa: "Synthesis and Spectroscopic Characterization of (Bu^n_4N)_5[(Cp^*Rh)_2P_2W_<15>V_3O_<62>]"Chem.Lett.. 410-411 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Acitve sites of vanadium-substituted POM catalysts on benzene hydroxylation"J.Mol.Catal.. A152. 55-68 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Benzene hydroxylation catalyzed by vanadium(V)-substituted POMs"J.Mol.Catal.. A156. 143-152 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis of the tetrameric, Dawson polyoxotungstate, [(P_2W_<15>Ti_3O_<60.5>)_4]^<36->"Inorg.Chim.Acta. 300-302. 285-304 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis of a Keggin polyoxotungstate [(Cp^*Rh)(α-1,4,9-PW_9V_3O_<40>]^<4->"J.Chem.Soc., Dalton Trans.. 52-56 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis and Characterization of the Water-Soluble, All-Inorganic Composition, Keggin-Type Triniobium (V)-Substituted SiW_9Nb_3O_<40>^<7-> Heteropolyanions with Alkali Metal Countercations (Li^+, Na^+, K^+ and Cs^+)"Bull.Chem.Soc.Jpn.. Vol.71. 2603-2610 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya and T.Hasegawa: "Synthesis and Spectroscopic Characterization of a Dawson Trivanadium-Substituted Polyoxotungstate-Supported {(Cp^*Rh)_2}^<4+> Complex : (Bu^n_4)_5 [(Cp^*Rh)_2P_2W_<15>V_3O_<62>]"Chem.Lett.. 410-411 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Multicenter active sites of vanadium-substituted polyoxometalate catalysts on benzene hydroxylation with hydrogen peroxide and two reaction types with and without an induction period"J.Mol.Catal.. Vol.A152. 55-68 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Benzene hydroxylation with hydrogen peroxide catalyzed by vanadium (V)-substituted polyoxomolybdates"J.Mol.Catal.. Vol.A156. 143-152 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis and characterization of the tetrameric, tri-titanium (IV)-substituted Wells-Dawson-substructure polyoxotungstate, [(P_2W_<15>Ti_3O_<60.5>)_4]^<36-> : the significance of ultracentrifugation molecular weight measurements in detecting aggregated, anhydride forms of polyoxoanions"Inorg.Chim.Acta. Vol.300-302. 285-304 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis and spectroscopic characterization of a Keggin α-1,4,9-trivanadium-substituted polyoxotungstate-supported Cp^*Rh^<2+> complex, [(Cp^*Rh)(α-1,4,9-PW_9V_3O_<40>)]^<4->"J.Chem.Soc., Dalton Trans.. 52-56 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Nomiya et al.: "Synthesis of Triuiobium(V)-Substituted SiW_9Nb_3O_<40>^<7-> Heteropolyoxoauions"Bull.Chem.Soc.Jpn.. 71(11). 2603-2610 (1998)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya and T.Hasegawa: "Synthesis and Spectroscopic Characterization of (Bu^n_4N)_5[(Cp^*Rh)_2P_2W_<15>V_30_<62>]"Chem.Lett.. 410-411 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya et al.: "Active sites of vanadium-substituted POM catalysts on benzene hydroxylation"J.Mol.Catal.. A152. 55-68 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya et al.: "Benzene hydroxylation catalyzed by vanadium(V)-substituted POMs"J.Mol.Catal.. A156. 143-152 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya et al.: "Synthesis of the tetrameric, Dawson polyoxotungstate, [(P_2W_<15>Ti_3O_<60.5>)_4]^<36->"Inorg.Chim.Acta. 300-302. 285-304 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya et al.: "Synthesis of a Keggin polyoxotungstate [(Cp^*Rh)(α-1,4,9-PW_9V_30_<40>]^<4->"J.Chem.Soc.,Dalton Trans.. 52-56 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Nomiya and T.Hasegawa: "Synthesis and Spectroscopic Characterization of(Bu^n_4 N)_5[(Cp^*Rh)_2P_2W_<15>V_3O_<62>]"Chem.Lett.,2000. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Nomiya et al: "Multicenter active sites of vanadium-substituted POM catalysts on benzene hydroxylation"J.Mol.Catal.,2000. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Nomiya et al: "Benzene hydroxylation with hydrogen peroxide catalyzed by vanadium(V)-substituted POMs"J.Mol.Catal.,2000. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Nomiya et al: "Synthesis and characterization of the tetrameric, Dawson polyoxotungstate,[P_2W_<15>Ti_3O_<60.5>)_4]^<36->"Inorg.Chim.Acta,2000. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Nomiya et al.: "Synthesis of Keggin-Type Triniobium(V)-Substituted SiW_9Nb_3O_<40>^<7-> Heteropolyoxoanions" Bull.Chem.Soc.Jpn.71(11). 2603-2610 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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