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複合金属シアン化物錯体触媒(DMC触媒)の活性空間の探求

Research Project

Project/Area Number 18033044
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka City University

Principal Investigator

中沢 浩  Osaka City University, 大学院・理学研究科, 教授 (00172297)

Co-Investigator(Kenkyū-buntansha) 板崎 真澄  大阪市立大学, 大学院・理学研究科, 講師 (60382032)
Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2007: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2006: ¥1,900,000 (Direct Cost: ¥1,900,000)
KeywordsDMC触媒 / プロピレンオキシド / 重合反応 / 亜鉛錯体 / 触媒反応 / ポリエーテルポリオール / 重合 / 助触媒
Research Abstract

複合金属シアン化物錯体触媒(DMC触媒)は多価アルコールにプロピレンオキシド(PO)などのエポキシドを重合させる触媒として知られているが,その真の触媒活性種や反応機構は現在まで明らかになっていない。本研究では亜鉛が触媒活性中心となっているとの推測のもと,種々のN-Nアミンキレート配位子をもつ亜鉛錯体である,ZnN_3Cl_2,[ZnN_4Cl]^+,ZnN_4]^<2+>タイプの錯体を合成し,POの重合活性を調べた。その結果AgN0_3やTMSOTfなどの助触媒をジクロロ錯体に対しては2当量,モノクロロ錯体に対しては1当量用いると触媒活性を示すことが明らかとなった。これより,[ZnN_3]^<2+>タイプの錯体が触媒活性を示すことが示唆された。
次に,N-Oキレート配位子を有する亜鉛錯体について検討した。8-ヒドロキシキノリンとZnEt_2との反応ではこの配位子が架橋した直線型3核および4核錯体が生成するのに対して,2-メチル8-ヒドロキシキノリンとZnEt^2との反応では面共有ダブルキュバン構造の対角2頂点が欠けた不完全ダブルキュバン構造の錯体が生成することをX線構造解析により明らかにした。この錯体は,溶液中では徐々に配位子架橋折れ曲がり型3核錯体へと変換するが,InBr_3との反応では8員環4核錯体が生成することがX線構造解析により明らかになった。PO重合触媒能については,不完全ダブルキュバン錯体は全く触媒能を示さないのに対して,8員環4核錯体については0.5mol%を使用して10gのPOがほぼすべて重合する高い触媒能を有することが明らかになった。

Report

(2 results)
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (35 results)

All 2008 2007 2006

All Journal Article (11 results) (of which Peer Reviewed: 7 results) Presentation (21 results) Patent(Industrial Property Rights) (3 results)

  • [Journal Article] Transition Metal Complexes Containing Phosphenium and Phosphite Ligands:Formation and Theoretical Approach2008

    • Author(s)
      H. Nakazawa, K. Miyoshi, and K. Takano
    • Journal Title

      Phosphorus, Sulfur, and Silicon, and the Related Elements (In press)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Molybdenum Complexes Bearing a Diaminosubstituted-Phosphiteboryl Ligand: Syntheses,Structures,and Reactivity Involving the Mo-B,B-P,and B-H Activation2007

    • Author(s)
      H. Nakazawa, M. Itazaki, and M. Ohba
    • Journal Title

      J. Organomet. Chem. 692

      Pages: 201-207

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Carbonyl(η^5-cyclopentadienyl)(3,5-dimethylpyridine-κN)(triethylsilyl)iron(II)2007

    • Author(s)
      M. Itazaki, K. Ueda, and H. Nakazawa
    • Journal Title

      Acta Cryst. E63

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iron-Complex-Catalyzed C-C Bond Cleavage of Organonitriles:Catalytic Metathesis Reaction between H-Si and R-CN Bonds to Afford R-H and Si-CN Bonds2007

    • Author(s)
      H. Nakazawa, M. Itazaki, K. Kamata, and K. Ueda
    • Journal Title

      Chem. Asian J. 2

      Pages: 882-888

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Silane-Catalyzed Reaction: Fac-mer Isomerization of [Mo(CO)_3(phosphite)_3]2007

    • Author(s)
      M. Tadokoro, T. Inoue, S. Tamaki, K. Fujii, H. Nakazawa, S. Takeda, K. Isobe, N. Koga, A. Ichimura, and K. Nakasuji
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 5938-5942

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Carbonyl(η^5-cyclopentadienyl)(3,5-dimethylpyridine-κN)(triethylsilyl)iron(II)2007

    • Author(s)
      K. Fukumoto and H. Nakazawa
    • Journal Title

      Organometallics 26

      Pages: 6505-6507

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reactivity of Hydridomolybdunum Complex Having Diamino-Substituted Phosphite Ligand with Me_3SiOSO_2CF_32007

    • Author(s)
      M. Itazaki and H. Nakazawa
    • Journal Title

      Phosphorus, Sulfur, and Silicon, and the Related Elements. (In press)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Molybdenum Complexes Bearing a Diaminosubstitued- phosphiteboryi Ligand : Syntheses, Structures, and Reactivity Involving the Mo-B, B-P, and B-H Activation2007

    • Author(s)
      H.Nakazawa
    • Journal Title

      J. Organomet. Chem. 692

      Pages: 201-207

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis and Reactivity of a Phosphite-Boryl Complex of Molybdenum : Formation of (η^5-C_5Me_5)Mo(CO)_3(BH_2-phsphite) and Its Mo-B, B-P, and B-H Bond Reactions2006

    • Author(s)
      H.Nakazawa
    • Journal Title

      Organometallics 25

      Pages: 2903-2905

    • Related Report
      2006 Annual Research Report
  • [Journal Article] fac-[Bis(2-pyridylmethyl)amine-k^5N]tribromoindium(III)2006

    • Author(s)
      M.Itazaki
    • Journal Title

      Acta Cryst. E62

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Syntheses, Structures, and DFT Calculations of Phosphenium Phosphite Complexes of Molybdenum : Preference of Non-bridging Form to Bridging Form of a Donor Group2006

    • Author(s)
      H.Nakazawa
    • Journal Title

      Organometallics 25

      Pages: 5913-5921

    • Related Report
      2006 Annual Research Report
  • [Presentation] 鉄錯体を触媒とする3級シランの脱水素カップリング反応2008

    • Author(s)
      板崎 真澄、植田 兼助、中沢 浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] 鉄触媒によるアルキンのヒドロゲルミル化学反応2008

    • Author(s)
      神谷 昌宏、植田 兼助、板崎 真澄、中沢 浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] シリル-鉄錯体を用いたN-CN結合活性化2008

    • Author(s)
      福本 晃造、大家 創、板崎 真澄、中沢 浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] 13族元素配位子をもつアニオン性錯体の合成と反応性2008

    • Author(s)
      能一 訓久、板崎 真澄、中沢 浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] シリル基を配位子とする鉄錯体が示す触媒作用2007

    • Author(s)
      中沢 浩
    • Organizer
      大阪市立大学重点研究分子精密制御の高次物質化学2007
    • Place of Presentation
      大阪市立大学
    • Year and Date
      2007-12-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] シリルピリジン鉄錯体Cp(CO)FeH(SiEt_3)(py)とEt_3EH(E=Si,Ge)との反応2007

    • Author(s)
      植田 兼助、神谷 昌宏、板崎 真澄、中沢 浩
    • Organizer
      第34回有機典型元素化学討論会
    • Place of Presentation
      大阪大学
    • Year and Date
      2007-12-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Si-Si Bond Formation from Hydrosilane Catalyzed by an Iron Complex2007

    • Author(s)
      K. Ueda, M. Itazaki, and H. Nakazawa
    • Organizer
      1st Asian Silicon Symposium
    • Place of Presentation
      Zao, Japan
    • Year and Date
      2007-11-02
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Reactivity of Disilyl- or Silylgermyl-lron(IV) Hydrido Complexes2007

    • Author(s)
      板崎 真澄、植田 兼助、神谷 昌宏、中沢 浩
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] N-CN Bond Cleavage of Cyanamides by an Iron Complex2007

    • Author(s)
      福本 晃造、大家 創、板崎真澄、中沢 浩
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] ホスフェニウム錯体とシリレン錯体の構造に関する量子化学的研究2007

    • Author(s)
      土田 敦子、中沢 浩、鷹野 景子
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] トリスピラゾリルボレート類を配位子とする6族遷移金属とインジウム間に結合をもつ錯体の合成と反応性2007

    • Author(s)
      板崎 真澄、能一 訓久、大熊 健一郎、中沢 浩
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] アシル基と3級リン化合物を配位子とするモリブデン錯体の合成とルイス酸との反応性2007

    • Author(s)
      二藤 久美子、福本 晃造、中沢 浩
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-25
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Reaction of Molybdenum Complexes Bearing Acyl and Terti Phos horus Ligands2007

    • Author(s)
      K. Nito, K. Fukumoto, and H. Nakazawa
    • Organizer
      The 11th Osaka City University International Conference -New Horizons of Molecular Science Dispached from Asia-
    • Place of Presentation
      Osaka, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Silicon Hypervalent Compounds Catalyzing Transition-metal Isomerization2007

    • Author(s)
      K. Fukumoto and H. Nakazawa
    • Organizer
      The 11th Osaka City University International Conference -New Horizons of Molecular Science Dispached from Asia-
    • Place of Presentation
      Osaka, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Facial to Meridional Isomerization of [Mo(CO)_3(phosphite)_3]Catalyzed by Halosilane2007

    • Author(s)
      K. Fukumoto and H. Nakazawa
    • Organizer
      The First Asian Conference on Coordination Chemistry
    • Place of Presentation
      Okazaki, Japan
    • Year and Date
      2007-07-31
    • Related Report
      2007 Annual Research Report
  • [Presentation] A DFT Study on Geometric Preference of Non-bridging Form to bridging Form of a Donor Group in Phosphenium Complexes2007

    • Author(s)
      N. Tsuchida, H. Nakazawa, and K. Takano
    • Organizer
      The First Asian Conference on Coordination Chemistry
    • Place of Presentation
      Okazaki, Japan
    • Year and Date
      2007-07-31
    • Related Report
      2007 Annual Research Report
  • [Presentation] Catalytic Bond Metathesis Reaction between C-CN and Si-H byan Iron Complex2007

    • Author(s)
      H. Nakazawa, M. Itazaki, and K. Kamata
    • Organizer
      The First Asian Conference on Coordination Chemistry
    • Place of Presentation
      Okazaki, Japan
    • Year and Date
      2007-07-30
    • Related Report
      2007 Annual Research Report
  • [Presentation] C-C Bond Cleavageof Organonitriles Catalyzedbyan Iron Silyl Complex2007

    • Author(s)
      H. Nakazawa
    • Organizer
      The 10th Osaka City University International Conference -Survey of Molecular Inortanic Chemistry-
    • Place of Presentation
      Osaka, Japan
    • Year and Date
      2007-07-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] ホスフェニウム錯体とシリレン錯体の構造に関する量子化学的研究2007

    • Author(s)
      土田 敦子、中沢 浩、鷹野 景子
    • Organizer
      日本コンピューター化学会2007春李年会
    • Place of Presentation
      東京工業大学
    • Year and Date
      2007-05-24
    • Related Report
      2007 Annual Research Report
  • [Presentation] ホスフェニウム錯体とシリレン錯体の構造に関する量子化学的研究2007

    • Author(s)
      土田 敦子、中沢 浩、鷹野 景子
    • Organizer
      第10回理論化掌討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2007-05-15
    • Related Report
      2007 Annual Research Report
  • [Presentation] Transition Metal Complexes Containing Phosphenium and Phosphite Ligands:Formation and Theoretical Approach2007

    • Author(s)
      H. Nakazawa, K. Miyoshi, and K. Tkano
    • Organizer
      17th International Conference on Phosphorus Chemistry
    • Place of Presentation
      Xiamen, China
    • Year and Date
      2007-04-16
    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 特許2007

    • Inventor(s)
      中沢 浩、板崎 真澄
    • Industrial Property Rights Holder
      中沢 浩、板崎 真澄
    • Filing Date
      2007-10-31
    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 特許2007

    • Inventor(s)
      中沢 浩、板崎 真澄
    • Industrial Property Rights Holder
      中沢 浩、板崎 真澄
    • Filing Date
      2007-10-31
    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 特許2007

    • Inventor(s)
      中沢 浩、板崎 真澄
    • Industrial Property Rights Holder
      中沢 浩、板崎 真澄
    • Filing Date
      2007-10-31
    • Related Report
      2007 Annual Research Report

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Published: 2006-04-01   Modified: 2018-03-28  

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