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Development of Epoxidation of Alkenes with Molecular Oxygen Catalyzed by Metal-substituted Polyoxometalates

Research Project

Project/Area Number 14350423
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 触媒・化学プロセス
Research InstitutionThe University of Tokyo

Principal Investigator

MIZUNO Noritaka  The University of Tokyo, Graduate School of Engineering, Research Associate, 大学院・工学系研究科, 教授 (50181904)

Co-Investigator(Kenkyū-buntansha) YAMAGUCHI Kazuya  The University of Tokyo, Graduate School of Engineering, Research Associate, 大学院・工学系研究科, 助手 (50334313)
HIKICHI Shiro  The University of Tokyo, Graduate School of Engineering, Associate Professor, 大学院・工学系研究科, 助教授 (10282857)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥17,100,000 (Direct Cost: ¥17,100,000)
Fiscal Year 2003: ¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 2002: ¥11,200,000 (Direct Cost: ¥11,200,000)
KeywordsPolyoxometalate / Molecular oxygen / Iron / Olefin epoxidation / Structure of catalvtically active site / 置換 / アルケン / 酸化
Research Abstract

(1) Lacunary POM as an efficient epoxidation catalyst with hydrogen peroxide.
The lacunary Keggin-type silicodecatungstate has been used as a catalyst precursor for epoxidation of olefins with H_2O_2 at 305 K. The catalytic epoxidation proceeded with【greater than or equal】 99% selectivity to epoxide, 【greater than or equal】99% efficiency of H_2O_2 utilization, high stereospecificity, and the easy recovery of the catalyst.
(2) Bis (μ-oxo) bridged di-Iron site on the lacunary POM as an efficient epoxidation catalyst with molecular oxygen.
Bis (オ-oxo) bridged di-iron site on the lacunary POM has been used as catalysts for the oxygenation of alkenes in homogeneous reaction media using molecular oxygen as an oxygen donor. It is remarkable that selectivity to cyclooctene oxide and turnover number reached up to 98% and 10000, respectively, for the oxygenation of cyclooctene. Not only cyclooctene but also cyclododecene, 1-octene, 2-octene, 2-heptene and 2-hexene were catalytically oxygenated with high turnover numbers and high selectivity to the corresponding epoxides.
(3) Microstructured POMs as a shape-selective catalyst.
Keggin-type polyoxometalate, SiW_<12>O_<40>^<4->, and Cr(III) trinuclear cation, Cr_3O(OOOCH)_6(H_2O)_3^+, assembled in the presence of K^+ to create a channeled complex K_3[Cr_3O(OOCH)_6(H_2O)_3]SiW_<12>O_<40>・16H_2O with an opening of 0.5 x 0.8 nm. The complex reversibly absorbs water and polar organic molecules smaller than C2. The guest inclusion was highly selective and even a difference of one methylene group in the organic guest molecule was discriminated. Polar organic molecules with longer methylene chain and non-polar molecules were completely excluded. The distinctive guest inclusion was successfully applied to the oxidation of methanol from a mixture of alcohols.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] K.Kamata, Y.Nakagawa, K.Yamaguchi, N.Mizuno: "Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW_<10>O_<34>(H_2O)_2]^<4->"J.Catal.. 224. 224-248 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Yamaguchi, S.Shinachi, N.Mizuno: "[VO(H_2O)_5]HPMo_<12>O_<40>-catalyzed nitration of alkanes with nitric acid"Chem.Commun. 1602-1603 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, K.Yamaguchi, S.Hikichi, N.Mizuno: "[{W(=O)(O_2)_2(H_2O)}_2(μ-O)]^<2->-Catalyzed Epoxidation of Allylic Alcohols in Water with High Selectivity and Utilization of Hydrogen Peroxide"Adv.Synth.Catal.. 345. 1193-1196 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, K.Yonehara, Y.Sumida, K.Yamaguchi, S.Hikichi, N.Mizuno: "Efficient Epoxidation of Olefins with 【greater than or equal】99% Selectivity and Use of Hydrogen Peroxide"Science. 300. 964-966 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Nishiyama, T.Hayashi, Y.Nakagawa, N.Mizuno: "A Green Route to Epoxide-Catalytic Selective Epoxidation of Alkenes with latm Molecular Oxygen with 10000 Turnover Number"Stud.Surf.Sci.Catal.. 145. 255-258 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Yamaguchi, N.Mizuno: "Efficient Heterogeneous Aerobic Oxidation of Amines by a Supported Ruthenium Catalyst"Angew.Chem.Int.Ed.Engl.. 42. 1480-1483 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, Y.Nakagawa, K.Yamaguchi, N.Mizuno: "Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW_<10>O_<34>(H_2O)_2]^<4->"J.Catal.. 224. 224-228 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Yamaguchi, S.Shinachi, N.Mizuno: "[VO(H_2O)_5]HPMo_<12>O_<40>-catalyzed nitration of alkanes with nitric acid"Chem.Commun. 1602-1603 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, K.Yamaguchi, S.Hikichi, N.Mizuno: "[{W(=O)(O_2)_2(H_2O)} 2(□-O)]^<-2> Catalyzed Epoxidation of Allylic Alcohols in Waterwith High Selectivity and Utilization of Hydrogen Peroxide"Adv.Synth.Catal. 345. 1193-1196 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, K.Yonehara, Y.Sumida, K.Yamaguchi, S.Hikichi, N.Mizuno: "Efficient Epoxidation of Olefins with 【greater than or equal】99% Selectivity and Use of Hydrogen Peroxide"Science. 300. 964-966 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Nishiyama, T.Hayashi, Y.Nakagawa, N.Mizuno: "A Green Route to Epoxide-Catalytic Selective Epoxidation of Alkenes with latm Molecular Oxygen with 10000 Turnover Number"Stud.Surf.Sci.Catal.. 145. 255-258 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Yamaguchi, N.Mizuno: "Efficient Heterogeneous Aerobic Oxidation of Amines by a Supported Ruthenium Catalyst"Angew.Chem.Int.Ed.Engl. 42. 1480-1483 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Kamata, Y.Nakagawa, K.Yamaguchi, N.Mizuno: "Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW_<10>O_<34>(H_2O)_2]^<4->"J.Catal.. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Yamaguchi, S.Shinachi, N.Mizuno: "[VO(H_2O)_5]HPMo_<12>O_<40>-catalyzed nitration of alkanes with nitric acid"Chem.Commun. 1602-1603 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kamata, K.Yamaguchi, S.Hikichi, N.Mizuno: "[{W(=O)(O_2)_2(H_2O)}_2(μ-O)]^<2->-Catalyzed Epoxidation of Allylic Alcohols in Water with High Selectivity and Utilization of Hydrogen Peroxide"Adv.Synth.Catal.. 345. 1193-1196 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kamata, K.Yonehara, Y.Sumida, K.Yamaguchi, S.Hikichi, N.Mizuno: "Efficient Epoxidation of Olefins with 【greater than or equal】99% Selectivity and Use of Hydrogen Peroxide"Science. 300. 964-966 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Nishiyama, T.Hayashi, Y.Nakagawa, N.Mizuno: "A Green Route to Epoxide-Catalytic Selective Epoxidation of Alkenes with 1atm Molecular Oxygen with 10000 Turnover Number"Stud.Surf.Sci.Catal.. 145. 255-258 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Yamaguchi, N.Mizuno: "Efficient Heterogeneous Aerobic Oxidation of Amines by a Supported Ruthenium Catalyst"Angew.Chem.Int.Ed.Engl.. 42. 1480-1483 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Yamaguchi et al.: "Heterogeneously Catalyzed Liquid-phase Oxidation of Alkanes and Alcohols with Molecular Oxygen"New.J.Chem.. 26. 972-974 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Mizuno et al.: "Selective Oxidation of Hydrocarbons with Molecular Oxygen Catalyzed by Transition-Metal-Substituted Silicotungstates"Polyoxometalate Chemistry for Nano-Composite Design. 197-203 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Yamaguchi et al.: "Supported Ruthenium Catalyst for the Heterogeneous Oxidation of Alcohols with Molecular Oxygen"Angew. Chem. Int. Ed.. 41/23. 4538-4542 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Mizuno: "Control of Structure of Oxide Cluster and the Application to Catalytic Technology"Int.J.Soc.Mater.Eng.Resour.. 10・2. 135-137 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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