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熱安定性多座配位子を有する低配位型触媒活性種の発生と応用

Publicly Offered Research

Project AreaMolecule Activation Directed toward Straightforward Synthesis
Project/Area Number 23105510
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

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

Principal Investigator

山下 誠  中央大学, 理工学部, 准教授 (10376486)

Project Period (FY) 2011 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2012: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Keywordsホウ素 / 多座配位子 / 低配位錯体 / 触媒
Research Abstract

平成24年度は以下の2種類の結果が得られた。
1.PBPピンサー配位子を有するPt錯体を用いたアルケンのヒドロシリル化反応の開発および新規配位子前駆体としてのジヒドロボラートの合成
昨年度の成果として得られたPBP-PtCl錯体をHSiEt_3および1-deceneと加熱することにより、ヒドロシリル化反応が進行して、トリメチルシリルデカンが得られることを発見した。反応機構を解析するため、ヒドリド錯体PBP-PtHを合成、単離して触媒反応に用いたところ、これを経由していないことがわかったため、典型的なChalk-Harrod型の機構で進行していることが明らかになった。一方で、このヒドリド錯体を二酸化炭素と反応させると、瞬時に反応して対応するPBP-Ptホルマト錯体に変換されることを見いだした。
また、PBP配位子前駆体として用いているヒドロボランに対してTHF中で水素化カリウムを作用させることで、ホウ素上に水素が2つ結合したジヒドロボラート型の化合物を合成、単離することに成功した。この化合物は結晶中でカリウム原子がジヒドロボラート部位とベンゾ縮環部位を架橋して、無限構造をとっていることが明らかになった。
2.Ru錯体触媒のみを用いたアルケンの直鎖選択的ヒドロホルミル化-水素化反応の開発
独自に合成したシクロペンタジエノンRu錯体に対してXantphos配位子を加えて、プロペンまたは1-デセンを合成ガスと反応させたところ、直鎖選択的ヒドロホルミル化反応が進行して直鎖アルデヒドが生成すると共に、このアルデヒドが水素化された直鎖アルコールが最高73%の収率で得られた。また、昨年度の成果として既報のRh-Xantphos/二核Ruの二元系触媒を用いたアルケンの直鎖選択的ヒドロホルミル化-水素化反応における反応速度論解析を行い、ヒドロホルミル化段階の反応速度はアルケン濃度に対して一次、水素化段階の反応速度はアルデヒド濃度に対して0次であることを明らかにした。

Report

(2 results)
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (24 results)

All 2012 2011 Other

All Journal Article (9 results) (of which Peer Reviewed: 9 results) Presentation (13 results) Remarks (2 results)

  • [Journal Article] Isolation of PBP-Pincer Rhodium Complex Stabilized by an Intermolecular C-H σ-Coordination as the Fourth Ligand2012

    • Author(s)
      Hasegawa, M.; Segawa, Y.; Yamashita, M.; Nozaki, K.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Issue: 28 Pages: 6956-6960

    • DOI

      10.1002/anie.201201916

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tandem Hydroformylation/Hydrogenation of Alkenes to normal-Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst2012

    • Author(s)
      Takahashi, K. ; Yanashita, M. ; Nozaki, K.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 134 Issue: 45 Pages: 18746-18757

    • DOI

      10.1021/ja307998h

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Platinum Complexes Bearing a Boron-Based PBP Pincer Ligand : Synthesis, Structure, and Application as a Catalyst for Hydrosilylation of 1-Decene2012

    • Author(s)
      Ogawa, H.; Yamashita, M.
    • Journal Title

      Dalton Trans.

      Volume: 46 Issue: 3 Pages: 625-629

    • DOI

      10.1039/c2dt31892j

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium/C5Me5/Bisphosphine- or Bisphosphite-Based Catalysts for normal-Selective Hydroformylation2012

    • Author(s)
      Takahashi, K.; Yamashita, Y.; Tanaka, Y.; Nozaki, K.
    • Journal Title

      Angewandte Chemie International Edition

      Volume: (印刷中)(掲載確定) Issue: 18 Pages: 4383-4387

    • DOI

      10.1002/anie.201108396

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Syntheses and Thermolysis of Arylpalladium Hydroxide Complexes : Implications for C(sp^2)-OH Bond-Forming Reductive Elimination to Generate Phenol Derivatives2012

    • Author(s)
      Hayashi, Y.; Wada, S.; Yamashita, M.; Nozaki, K.
    • Journal Title

      Organometallics

      Volume: 31 Issue: 3 Pages: 1073-1081

    • DOI

      10.1021/om201142s

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanistic Studies on the Reversible Hydrogenation of Carbon Dioxide Catalyzed2011

    • Author(s)
      R.Tanaka, M.Yamashita, L.W.Chung, K.Morokuma, K.Nozaki
    • Journal Title

      Organometallies

      Volume: 30 Issue: 24 Pages: 6742-6750

    • DOI

      10.1021/om2010172

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Borylcyanocuprate in a One-Pot Carboboration by a Sequential Reaction with an Electron-Deficient Alkyne and an Organic Carbon Electrophile2011

    • Author(s)
      Okuno, Y.; Yamashita, M.; Nozaki, K.
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 50 Issue: 4 Pages: 920-923

    • DOI

      10.1002/anie.201005667

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Syntheses and Properties of Triborane(5)s Possessing Bulky Diamino Substituents on Terminal Boron Atoms2011

    • Author(s)
      Hayashi, Y.; Segawa, Y.; Yamashita, M.; Nozaki, K.
    • Journal Title

      Chem.Commun.

      Volume: 47 Issue: 20 Pages: 5888-5890

    • DOI

      10.1039/c1cc11334h

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Carboboration of Alkynes Using Lithium Borylcyanocuprate and the Subsequent Suzuki-Miyaura Cross-Coupling Reaction of Resulting Tetrasubstituted Alkenylborane2011

    • Author(s)
      Okuno, Y.; Yamashita, M.; Nozaki, K.
    • Journal Title

      Eur.J.Org.Chem.

      Volume: 2011 Issue: 20-21 Pages: 3951-3958

    • DOI

      10.1002/ejoc.201100373

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] Syntheses, Properties, and Catalytic Performance of Late-Transition Metal Complexes Bearing A Characteristic Multidentate Ligand2012

    • Author(s)
      Makoto Yamashita
    • Organizer
      8th RIKEN International Symposium "Frontiers of Organometallic Chemistry"
    • Place of Presentation
      理化学研究所
    • Year and Date
      2012-11-30
    • Related Report
      2012 Annual Research Report
  • [Presentation] PBPピンサー型配位子を有する白金錯体の合成と性質2012

    • Author(s)
      小川隼人, 山下誠
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      富山大学
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report
  • [Presentation] PBPピンサーRu錯体の合成と性質2012

    • Author(s)
      宮田卓真, 山下誠
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      富山大学
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Properties of Late Transition Metal Complexes Bearing a PBP-Pincer Ligand2012

    • Author(s)
      Makoto Yamashita
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      富山大学
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report
  • [Presentation] Synthesis and Properties of Potassium Diaminodihydroborate with Two Tethers2012

    • Author(s)
      Takuma Miyada, Makoto Yamashita
    • Organizer
      25th International Conference on Organometallic Chemistry
    • Place of Presentation
      リスボン大学
    • Year and Date
      2012-09-03
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Properties of Platinum Complexes Bearing a PBP-Pincer Ligand2012

    • Author(s)
      Hayato Ogawa, Makoto Yamashita
    • Organizer
      25th International Conference on Organometallic Chemistry
    • Place of Presentation
      リスボン大学
    • Year and Date
      2012-09-03
    • Related Report
      2012 Annual Research Report
  • [Presentation] Tandem Hydroformylation/Hydrogenation of Terminal Alkenes to n-Alcohol Using a Rh/Ru Dual Catalyst System2012

    • Author(s)
      Kohei Takahashi, Makoto Yamashita, Kyoko Nozaki
    • Organizer
      25th International Conference on Organometallic Chemistry
    • Place of Presentation
      リスボン大学
    • Year and Date
      2012-09-03
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Properties of Late Transition Metal Complexes Bearing a Boron-Based PBP-Pincer Ligand : Effect of Boron Atom2012

    • Author(s)
      Makoto Yamashita
    • Organizer
      25th International Conference on Organometallic Chemistry
    • Place of Presentation
      リスボン大学
    • Year and Date
      2012-09-03
    • Related Report
      2012 Annual Research Report
  • [Presentation] ネオペンチル置換PCPピンサー型配位子を有するイリジウム錯体の合成と炭化水素の脱水素化反応へ向けた応用2011

    • Author(s)
      谷口諒・山下誠・野崎京子
    • Organizer
      第61回錯体化学討論会
    • Place of Presentation
      岡山理科大学
    • Year and Date
      2011-09-17
    • Related Report
      2011 Annual Research Report
  • [Presentation] Syntheses and properties of transition metal complexes bearing a boron-based PBP-pincer ligand2011

    • Author(s)
      Makoto Yamashita
    • Organizer
      IUPAC World Chemistry Congress
    • Place of Presentation
      Puerto Rico
    • Year and Date
      2011-08-02
    • Related Report
      2011 Annual Research Report
  • [Presentation] Rational Design of Ru-Catallysts for normal-Selective Hydroformylation and Tandem Hydroformylation/Hydrogenation2011

    • Author(s)
      高橋講平・山下誠・田中善幸・野崎京子
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学千種キャンパス
    • Related Report
      2011 Annual Research Report
  • [Presentation] Synthesis and Properties of Lithium Boryltrihydroborate2011

    • Author(s)
      Yoshitaka Aramaki, Makoto Yamashita, Shau-Hua Ueng, Max Maracria, Emmanuel Lacote, Dennis P.Curran, Kyoko Nozaki
    • Organizer
      IME Boron XIV
    • Place of Presentation
      Naiagarafalls
    • Related Report
      2011 Annual Research Report
  • [Presentation] Syntheses and properties of transition metal complexes bearing a boron-based PBP-pincer ligand2011

    • Author(s)
      Makoto Yamashita
    • Organizer
      IME Boron XIV
    • Place of Presentation
      Naiagarafalls
    • Related Report
      2011 Annual Research Report
  • [Remarks]

    • URL

      http://www.chem.chuo-u.ac.jp/~element/

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

      http://www.chem.chuo-u.ac.jp/~element/

    • Related Report
      2011 Annual Research Report

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Published: 2011-04-06   Modified: 2019-07-29  

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