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Development and Application of Novel Metal Catalysts with Steritically Hindered Ligand Systems

Research Project

Project/Area Number 13555257
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 高分子合成
Research InstitutionUniversity of Tsukuba

Principal Investigator

FUJISAWA Kiyoshi  University of Tsukuba, Graduate School of Pure and Applied Science, Associate Professor, 化学系, 助教授 (10251670)

Co-Investigator(Kenkyū-buntansha) ODA Yoshiaki  Sumitomo Chemical Co.Ltd, Researcher, 技術・経営企画室, 主席研究員
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2003: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2002: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2001: ¥10,700,000 (Direct Cost: ¥10,700,000)
Keywordshomogeneous catalysis / transition metal complex / dioxygen complex / polymerization of olefins / spectroscopic anal analysis / electronic structure / reaction mechanism / catalytic reaction
Research Abstract

1.Manganese complexes have the catalytic reaction properties for olefin polymerization reactions. This metal has not been paid any attentions. In order to get more insight on the reaction mechanism, we are now synthesizing manganese(II)-alkyl complexes
2.We characterized the pyrazolato complexes with steritically hindered pyrazolate ions. By use of these complexes, we explored an asymmetric conjugate addition reaction
3.The μ,-η^2 : η^2-disulfido complex was obtained by the reaction of the copper(I) complex with elemental sulfur. Its detailed electronic structure was examined
4.Mononuclear iron(II) α-keto and carboxylate compounds were prepared as models for the active sites of nonheme iron oxygenases. The α-keto acid carboxylate complexes react 2 orders of magnitude faster than the carboxylate complexes, thus emphasizing the key role that the α-keto functionality plays in oxygen activation by α-keto acid-dependent iron enzymes
5.The copper(I) complexes were prepared by using the novel stertically hindered tirs(pyrazolyl)methane ligands. We also compared the structures and properties between hydrotris(pyrazolyl)borate systems and tris(pyrazolyl)methane systems

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (43 results)

All Other

All Publications (43 results)

  • [Publications] K.Fujisawa, Y.Miyashita, Y.Yamada, K.Okamoto: "Structural Effects on Nitratocopper(II) Complexes of Tris(pyrazolyl)borates"Bull.Chem.Soc.Jpn.. 74. 1065-1066 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] D.Baba, H.Ishii, S.Higashiya, K.Fujisawa, T.Fuchigami: "Electroytic Partial Fluorination of Organic Compounds. 52.1 Regio- and Diastereoselective Anodic Fluorination of Thiazolidines"J.Org.Chem.. 66. 7020-7024 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Basumallick, S.D.George, D.W.Randall, K.Fujisawa, E.I.Solomon: "Spectroscopic Comparison of the 5-Coordinate [Cu(SMeIm)(HB(3,5-iPr_2pz)_3] with the 4-Coordinate [Cu(SCPh_3)(HB(3,5-iPr_2pz)_3] : Effect of Coordination Number Increase on a Blue Copper Type Site."Inorg.Chim.Acta. 337. 357-365 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Miyashita, M.Sanada, Y.Yamada, K.Fujisawa, K.Okamoto: "Novel Alkoxo-Bridged Lanthanide(III) Dinuclear Complexes : Crystal Structure of Na_4[Yb_2(μ-dpta-O)_2](N_4dpta-OH=1,3-Diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid)"Chem.Lett. 840-841 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] P.Chen, D.E.Root, C.Campochiaro, K.Fujisawa, E.I.Solomon: "Spectroscopic and Electronic Structure Studied of the Diamagnetic Side-On Cu^<II>-Superoxo Complex Cu(O_2)[HB{3-R-5-iPrpz)_3] : Antiferromagnetic Coupling vs.Covalent Delocalization"J Am.Chem.Soc.. 125. 466-474 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Lehnert, K.Fujisawa, E.I.Solomon: "Electronic Structure and Reactivity of High-spin Iron-Alkyl- and -Pterinperoxo Complexes"Inorg.Chem.. 42. 469-481 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] P.Chen, K.Fujisawa, M.E.Helton, K.D.Karlin, E.I.Solomon: "Spectroscopy and Bonding in Side-On and End-On Cu_2(S_2) Cores : Comparison to Peroxide Analogues"J.Am.Chem.Soc.. 125. 6394-6408 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.P.Mehn, K.Fujisawa, E.L.Hegg, L.Que, Jr.: "Oxygen Activation by Nonhem Iron(II) Complexes : α-Keto Carboxylate versus Carboxylate"J.Am.Chem.Soc.. 125. 7828-7842 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] C.Kashima, H.Yokoyama, S.Shibata, K.Fujisawa, T.Nishio: "Asymmetric Conjugate Addition Reaction Using Pyrazole Derivatives as a Chiral Catalyst"J.Heterocycl.Chem.. 40. 717-719 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, N.Tada, Y.Ishikawa, H.Higashimura, K.Okamoto: "The most hindered hydrotris(pyrazolyl)borate ligand ; X-ray structures of chlorocopper(II) complexes : [Cu(Cl){HB(3-Ad-5-Pr^ipz)_3}] as Compared with [Cu(Cl){HB(3-Bu^t-5-Pr^ipz)_3}]"Inorg.Chem.Commun.. 7. 209-212 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, T.Ono, H.Aoki, Y.Ishikawa, K.Okamoto, H.Nakazawa, H.Higashimura: "Copper(II) Complexes with a Novel Tris(3,5-diisopropyl-1-pyrazolyl)methane Ligand"Inorg.Chem.Commun.. 7. 330-332 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, Y.Ishikawa, Y.Miyashita, K.Okamoto: "Crystal Structure of Pyrazolato-Brideged Copper(I) Polynuclear Complexes"Chem.Lett.. 33. 66-67 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, Y.Miyashita, Y.Yamada, K.Okamoto: "Structural Effects on Nitratocopper (II) Complexes of Tris(pyrazolyl)borates"Bull.Chem.Soc.Jpn.. 74. 1065-1066 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] D.Baba, H.Ishii, S.Higashiya, K.Fujisawa, T.Fuchigami: "Electroytic Partial Fluorination of Organic Compounds. 52.1 Regio-and Diastereoselective Anodic Fluorination of Thiazolidines"J.Org.Chem.. 66. 7020-7024 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Basumallick, S.D.George, D.W.Randall.B.Hedman, K.O.Hodgson, K.Fujisawa, E.I.Solomon: "Spectroscopic Comparison of the 5-Coordinate [Cu(SMeIm)(HB(3,5iPr_2pz)_3] with the 4-Coordinate (Cu(SCPh_3)(HII(3,5-iPr_2pz)_3] : Effect of Coordination Number Increase on a Blue Copper ape Site"Inorg.Chim.Acta. 337. 357-365 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Miyashita, M.Sarnpda, Y.Yamada, K.Fujisawa, K.Okamoto: "Novel Alkoxo-Bridged Lanthanide(III) binuclear Complexes : Crystal Structure of Na_4[Yb_2(μ,-dpta-O)_2](N_4dpta-OH=1,3-Diamino-2hydroxypropane-N,N,N',N'-tetraacetic acid)"Chem.Lett.. 840-841 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] P.Chen, D.E.Roat, C.Campochiaro, K.Fujisawa, E.I.Solomon: "Spectroscopic and Electronic Structure Studied of the Diamagnetic Side-On Cu^<II>-Superoxo Complex Cu(O_2)(HB{3-R-5-^iPrpz)_3] : Anti-ferromagnetic Coupling vs. Covalent Delocalization"J.Am.Chem.Soc.. 125. 466-474 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Lehnert, K.Fujisawa, E.I.Solomon: "Electronic Structure and Reactivity of High-spin Iron-Alkyl and Pterinperoxo Complexes"Inogh.Chem.. 42. 469-481 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] P.Chen, K.Fujisawa, M.E.Helton, K.D.Karlin, E.I.Solomon: "Spectroscopy and Bonding in Side-On and End-On Cu_2(S_2) Cores : Comparison to Peroxide Analogues"J.Am.Chem.Soc.. 125. 6394-6408 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.P.Mehn, K.Fujisawa, E.L.Hegg, L.Que, Jr.: "Oxygen Activation by Nonhem Iron(II) Complexes : a-Keto Carboxylate versus Carboxylate"J.Am.Chem.Soc.. 125. 7828-7842 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] C.Kashima, H.Yokoyama, S.Shibata, K.Fujisawa, T.Nishio: "Asymmetric Conjugate Addition Reaction Using Pyrazole Derivatives as a Chiral Catalyst"J.Heterocycl.Chem.. 40. 717-719 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, N.Tada, Y.Ishikawa, H.Higashimura, Y.Miyashita, K.Okamoto: "The Most Hindered Hydrotris(Pyrazolyl)Borate Ligand ; X-Ray Structures of Chlorocopper(II) Complexes : [Cu(Cl){HB(3-Ad-5-Pr^ipz)_3}] as compared with [Cu(Cl){HB(3-Bu^t-5-Pr^ipz)_3}]"Inog.Chem.Commun.. 7. 209-212 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, T.Ono, H.Aoki, Y.Ishikawa, Y.Miyashita, K.Okamoto, H.Nakazawa, H.Higashimura: "Copper(II) Complexes with a Novel Tris(3,5-diisopropyi-1-pyrazolyl)methane Ligand"Inog.Chem.Commun.. 7. 330-332 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Fujisawa, Y.Ishikawa, Y.Miyashita, K.Okamoto: "Crystal Structure of Pyrazolato-Brideged Copper(I) Polynuclear Complexes"Chem.Lett.. 33. 66-67 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] P.Chen, K.Fujisawa, M.E.Helton, K.D.Karlin, E.I.Solomon: "Spectroscopy and Bonding in Side-On and End-On Cu_2(S_2) Cores : Comparison to Peroxide Analogues"J.Am.Chem.Soc.. 125. 6394-6408 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.P.Mehn, K.Fujisawa, E.L.Hegg, L.Que, Jr.: "Oxygen Activation by Nonhem Iron(II) Complexes : α-Keto Carboxylate versus Carboxylate"J.Am.Chem.Soc.. 125. 7828-7842 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] C.Kashima, H.Yokoyama, S.Shibata, K.Fujisawa, T.Nishio: "Asymmetric Conjugate Addition Reaction Using Pyrazole Derivatives as a Chiral Catalyst"J.Heterocycl.Chem.. 40. 717-719 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Fujisawa, N.Tada, Y.Ishikawa, H.Higashimura, Y.Miyashita, K.Okamoto: "The most hindered hydrotris(pyrazolyl)borate ligand ; X-ray structures of chlorocopper(II) complexes : [(Cu(CI){HB(3-Ad-5-Pr′pz)_3}] as compared with [Cu(Cl){HB(3-Bu′-5-Pr′pz)_3}]"Inorg.Chem.Commun.. 7. 209-212 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Fujisawa, T.Ono, H.Aoki, Y.Ishikawa, Y.Miyashita, K.Okamoto, H.Nakazawa, H.Higashimura: "Copper(II) Complexes with a Novel Tris(3,5-diisopropyl-1-pyrazolyl)methane Ligand"Inorg.Chem.Commun.. 7. 330-332 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Fujisawa, Y.Ishikawa, Y.Miyashita, K.Okamoto: "Crystal Structure of Pyrazolato-Brideged Copper(I) Polynuclear Complexes"Chem.Lett.. 33. 66-67 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] L Basumallick, S.D.George, D.W.Randall.B.Hedman, K.O.Hodgson, K.Fujisawa, E.I.Solomon: "Spectroscopic Comparison of the 5-Coordinate [Cu(SMelm)(HB(3,5-iPr_2pz)_3] with the 4-Coordinate (Cu(SCPh_3)(HB(3,5-iPr_2pz)_3] : Effect of Coordination Number Increase on a Blue Copper Type Site"Inorg.Chim.Acta. 337. 357-365 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Miyashita, M.Sanada, Y.Yamada, K.Fujisawa, K.Okamoto: "Novel Alkoxo-Bridged Lanthanide(III) Dinuclear Complexes : Crystal Structure of Na_4[Yb_2(_-dpta-O)_2](N_4dpta-OH = 1,3-Diamino-2-hydroxypropane-N, N, N' N' -tetraacetic acid)"Chem.Lett. 840-841 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] P.Chen, D.E.Root, C.Campochiaro, K.Fujisawa, E.I.Solomon: "Spectroscopic and Electronic Structure Studied of the Diamagnetic Side-On Cu^<II>-Superoxo Complex Cu(O_2)[HB{3-R-5-iPrpz)_3] : Antiferromagnetic Coupling vs. Covalent Delocalization"J Am.Chem.Soc.. 125. 466-474 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Lehnert, K.Fujisawa, E.I.Solomon: "Electronic Structure and Reactivity of High-spin Iron-Alkyl-and -Pterinperoxo Complexes"Inorg.Chem.. 42. 469-481 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] P.Chen, K.Fujisawa, M.E.Helton, K.D.Karlin, E.I.Solomon: "Spectroscopy and Bonding in Side-On and End-On Cu_2(S_2) Cores : Comparison to Peroxide Analogues"J.Am.Chem.Soc.. 125(印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.P.Mehn, K.Fujisawa, E.L.Hegg, L.Que, Jr.: "Oxygen Activation by Nonhem Iron(II) Complexes : α-Keto Carboxylate versus Carboxylate"J.Am.Chem.Soc.. 125(印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 藤澤 清史: "新版 錯体化学 基礎と最新の話題"基礎錯体工学研究会 編 分担 講談社サイエンティフク. 2 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Fujisawa, Y.Miyashita, Y.Yamada, K.Okamoto: "Structural Effects on Nitratocopper(II) Complexes of Tris(pyrazolyl)borates"Bull. Chem. Soc. Jpn.. 74. 1065-1066 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Miyashita, N.Mahboob, S.Tsuboi, Y.Yamada, K.Fujisawa, K.Okamoto: "fac-Trichloro(quinolin-8-ylimido-N,N')(triphenylphosphine-P)rhenium(V)"Acta Cryst.. C57. 558-559 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Miyashita, N.Mahboob, S.Tsuboi, Y.Yamada, K.Fujisawa, K.Okamoto: "Crystal Structure and Spectroscopic Characterization of Linear-Type S-Brideged Trinuclear Complexes ∧∧-and ∧∧/∧∧-[Re^<III>{Rh^<III>(aet)_3}^<3+> (aet=2-Aminoethanethiolate)"Bull. Chem. Soc. Jpn.. 74. 1295-1301 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Miyashita, M.Hamajima, Y.Yamada, K.Fujisawa, K.Okamoto: "Synthesis, Characterization and Reactivity of Linear-Type S-Brideged Trinuclear Complexes Containing Vanadium(III)ion. Crystal Structure of [V^<III>{M(aet)_3}_2](CIO_4)_3(M=Rh , Ir , aet=2-Aminoethanetholate)"J. Chem. Soc., Dalton Trans.. 2089-2094 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] D.Baba, H.Ishii, S.Higashiya, K.Fujisawa, T.Fuchigami: "Electroytic Partial Fluorination of Organic Compounds.52.1 Regio- and Diastereoselective Anodic Fluorination of Thiazolidines"J. Org. Chem.. 66. 7020-7024 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Miyashita, S.Arai, Y.Yamada, K.Fujisawa, K.Okamoto: "anti-Bis(μ-2-ammonioethanethiolato-κ^2S:S)bis[dichloropalladium(II)]dihydrate"Acta Cryst.. C57. 1393-1394 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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