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REACTION FIELD CREATED BY METAL COMPLEXES

Research Project

Project/Area Number 07305039
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section総合
Research Field Synthetic chemistry
Research InstitutionTOKYO INSTITUTE OF TECHNOLOGY

Principal Investigator

SUZUKI Hiroharu  Tokyo Institute of Technology, Professor, 工学部, 教授 (30106629)

Co-Investigator(Kenkyū-buntansha) KOMIYA Sanshiro  Tokyo University of Agriculture and Technology, Professor, 工学部, 教授 (00111667)
TATSUMI Kazuyuki  Nagoya University, Professor, 理学部, 教授 (10155096)
SAKAKI Shigeyoshi  Kumamoto University, Professor, 工学部, 教授 (20094013)
ISOBE Kiyoshi  Osaka City University, Professor, 理学部, 教授 (70101285)
ITO Takashi  Yokohama National University, Professor, 工学部, 教授 (50016721)
KOGA Nobuaki  Nagoya University, Associate Professor (80186650)
WAKATSUKI Yosuo  The Institute of Physial and Chemical Research, Research Manager (20087513)
TAKAHASHI Tamotsu  Hokkaido University, Professor (30163273)
OSAKADA Kohtaro  Tokyo Institute of Technology, Associate Professor (00152455)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1996: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1995: ¥4,000,000 (Direct Cost: ¥4,000,000)
KeywordsReaction Field / Polyhydride Complex / Dinuclear Complex / Trinuclear Complex / Metal Cluster / Coordinative Unsaturation / 金属錯体反応場 / 配位不飽和 / 多核錯体 / 二酸化炭素の固定化 / 炭素-イオウ結合活性化
Research Abstract

This research project was intended to establish the methodology for the construction and modification of the reaction field of metal complex. The reaction field created on the metal complex can be modified by appropriately changing ligands. Ten researchers working in a variety of fields have been divided into the following four groups.
1. Creation of Highly Functioned Mononuclear Active Species
Takashi ito, Kohtaro Osakada, and Sanshiro Komiya
2. Construction of Sterically and Electronically Controlled Multimetallic Reaction Field
Hiroharu Suzuki, Kiyashi Isobe, and Kazuyuki Tatsumi
3. Conversion of Organic Substrates in the Highly Controlled Metal Complex Reaction Field
Tamotu Takahashi and Yasuo Wakatsuki
4.Theoretical Approach directed toward Control of Reaction Field
Nobuaki Koga and Shigeyoshi Sakaki
The first group achieved activation of CO_2, Si-C bond, and N-H bond by using coordinatively unsaturated transition metal complexes. The second group developed systematic synthetic method of metal cluster complexes. Di- and trinuclear polyhydride complexes of ruthenium could activate a variety of organic substrates including alkanes and unprecedented type of selective C-H and C-C bonds cleavage was performed. A new class of clusters with Rh-S-W framework were systematically synthesized. A novel organic transformation involving zirconacyclopentene as synthetic intermediate and redox reaction of NO on hexanuclear carbonyl clusters were performed by the third group. Ab initio MO studies of several transition metal complex-catalyzed reactions such as olefin polymerization and hydrosilation were done by the fourth group.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] T.Takemori,H.Suzuki: "Formation of Novel Trinuclear μ_3-S-cis-η^2:η^2-1,3-Diene Complexes of Ruthenium Having an Agostic Ru-H-C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers." Organometallics. 15・21. 4346-4348 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Minato,H.Aakai,Z.Weng,D.Zhou,S.Kurishima,T.Ito: "Syntheses,Structures,and Reactions of η^2-N-Acylamido-N,OHydrido Complexes of Molybdenum (II) and Tungsten (II)" Organometallics. 15・22. 4863-4871 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Ogo,T.suzuki,Y.Ozawa,K.Isobe: "Structures,Bonding,and Reactivity of M-S-M' (M and M'=Rh,W,and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters" Inorganic Chemistry. 35・21. 6093-6101 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Sakaki,H.Satoh,H.Shono,Y.Ujino: "Ab Initio MO Study of the Geometry η^3⇔η^1 Conversion,and Reductive Elimination of a Palladium (II) η^3-Allyl Hydride Complex and Its Platinum (II) Analogue" Organometallics. 15・6. 1713-1720 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Lang,K.Tatsumi,H.Kawaguchi,J.Lu,P.Ge,W.Ji,S.Shi: "Microwave Irradiation Synthesis of Mo (W)/TI/S Linear Chains and Their Nonlinear Optical Properties in Solution" Inorganic Chemistry. 35・26. 7924-7927 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Murahashi,T.Naota,H.Taki,H.Takaya,S.Komiya,Y.Mizuno,M.Hiraoka,M.Hirano,A.Fukuoka: "Ruthenium-Catalyzed Aldol and Michael Reactions of Nitriles. Carbon-Carbon Bond Formaion by α-C-H Activation of Nitriles" Journal of the American Chemical Society. 117・50. 12436-12541 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Toshifumi Takemori, Hiroharu Suzuki, and Masako Tanaka: "Formation of Novel Trinuclear mu_3-s-cis-eta^2 : eta^2-1,3-Diene Complexes of Ruthenium Having Agostic Ru-H-C Interaction. A Direct Evidence for the Diene Activation in Cooperatin with Three Metal Centers" Organometallics. 15. 4346-4348 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Makoto Minato, Hiroyuki Sakai, Zu-Gan Weng, Da-Yang Zhou, Susumu Kurishima, Takashi Ito, Mikio Yamasaki, Motoo Shiro, Masako Tanaka and Kohtaro Osakada: "Syntheses, Ctructures, and Reactions of eta^2-N-Acylamido-N,O Hydrido Complexes of Molybdenum (II) and Tungsten" Organometallics. 15(22). 4863-4871 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Seiji Ogo, Takayoshi Suzuki, Yosiki Ozawa, and Kiyoshi Isobe: "Structures, Bonding and Reactivity of M-S-M' (M and M'=Rh, W,and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters" Inorg.Chem.35. 6093-6101 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Shigeyoshi Sakaki, Hiroyuki Satoh, Hiroshi Shono, and Yuka Ujino: "Ab Initio MO Study of the Geometry, eta^3-ml Conversion, and Reductive Elimination of a Palladium (II) eta^3-Allyl Hydride Complex and its Platinum Analogue" Organometallics. 15(6). 1713-1720 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Jianping Lang, Kazuyuki Tatsumi, Hiroyuki Kawaguchi, Jianmei Lu, Ping Ge, Wei Ji, and Shu Shin: "Microwave Irradiation Synthesis of Mo (W) /TI/S Linear Chains and Their Nonlinear Optical Properties in Solution" Inorg.Chem.35. 7924-7927 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Shun-ichi Murahashi, Takeshi Nota, Hiroshi Taki, Masahiko Mizuno, Hiraku Takaya, Sanshiro Komiya, Yuji Mizuho, Makiko Hiraoka, Masafumi Hirano, and Atsushi Fukuoka: "Ruthenium-Catalyzed Aldol and Michael Reactions of Nitriles. Carbon-Carbon Bond Formation by Alpha-C-H Activation of Nitriles" J.Am.Chem.Soc.117. 12436-12451 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Takemori,H.Suzuki: "Formation of Novel Trinuclear μ_3-S-cis-η^2:η^2-1,3-Diene Complexes of Ruthenium Having an Agostic Ru-H-C Interaction. Direct Evidence for Dine Activation in Cooperation with the Three Metal Centers." Organometallics. 15・21. 4346-4348 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Minato,H.Sakai,Z.Weng,D.Zhou,S.Kurishima,T.Ito: "Syntheses,Structures,and Reactions of η^2-N-Acylamido-N,O Hydrido Complexes of Molybdenum(II) and Tungsten(II)" Organometallics. 15・22. 4863-4871 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Ogo,T.Suzuki,Y.Ozawa,K.Isobe: "Structures,Bonding,and Reactivity of M-S-M′(M and M′=Rh,W,and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters" Inorganic Chemistry. 35・21. 6093-6101 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Sakaki,H.Satoh,H.Shono,Y.Ujino: "Ab Initio MO Study of the Geometry,η^3⇔η^1 Conversion,and Reductive Elimination of a Palladium(II) η^3-Allyl Hydride Complex and Its Platinum(II) Analogue" Organometallics. 15・6. 1713-1720 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Lang,K.Tatsumi,H.Kawaguchi J.Lu,P.Ge,W.Ji,S.Shi: "Microwave Irradiation Synthesis of Mo(W)/TI/S Linear Chains and Their Nonlinear Optical Properties in Solution" Inorganic Chemistry. 35/26. 7924-7927 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Murahashi,T.Naota.H.Taki,H.Takaya,S.Komiya,Y.Mizuho,M.Hiraoka,M.Hirano,A.Fukuoka: "Ruthenium-Catalyzed Aldol and Michael Reactions of Nitriles.Carbon-Carbon Bond Formation by α-C-H Activation of Nitriles" Journal of the American Chemical Society. 117・50. 12436-12451 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] T. Takao, S. Yoshida, H. Suzuki M. Tanaka: "Synthesis, Characterization, and Reactivities of Diruthenium Complexes Containing a μ-Silane Ligand and Structural Studies of the μ-Silane Complex [Cp′Ru(CO)]_2(μ-η^2-: η^2-H_2Si^lBu_2)" Organometallics. 14. 3855-3868 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S. Sakaki, Y. Musashi: "Ab-Initio Mo Study of the CO_2 Insertion into the Cu(I)-R Bond(R=H, CH_3, or OH)-Comparison Between the CO_2 Insertion and the C_2H_4 Insertion" Inorg. Chem.34. 1914-1923 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S. Sakaki, M. Ogawa, M. Kinoshita: "A Theoretical-Study on the Oxidative Addition of an Si-X Bond (X=H or Si) to M(PH3)2(M=Pd or Pt)-A Comparison of the Reactivity Berween Pt(PH3)2 and Pd(PH_3)_2" J. Phys. Chem.99. 9933-9939 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Z.Hou, T. Miyano, H. Yamazaki, Y. Wakatsuki: "The First Structurally Characterized Metal Ketyl Complex-Sm(Ketyl)(OAr)2(thf)2 and Its Reversible Coupling to a Disamarium(III)Pinacolate" J. Am. Chem. Soc.117. 4421-4422 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Z. Hou, K. Aida, Y. Takagi Y. Wakatsuki: "Synthesis and X-Ray Structure of the Divalent and Trivalent Ytterbium-Molybdenum Complexes Yb(II)(hmpa)_4(μ-OCMo(Co)_2Cp)_2 and (Yb(III)(hmpa)_5(μ-OCMo(CO)_2Cp)(CpMo(CO)_3)_2・THF" J. Organomet. Chem.487. C29-C29 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Ito, L. M. Wan, M. Minato: "Synthesis and Some Reactions of Molybdenocene Derivatives Coordinated with the Chiral Carboxylato Ligands" Bull. Chem. Soc. Jpn.69. 417-423 (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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