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Rearrangement of transition metal atom core and structural change and properties change of the framework

Research Project

Project/Area Number 24350027
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

OSAKADA Kohtaro  東京工業大学, 資源化学研究所, 教授 (00152455)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
Fiscal Year 2014: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2013: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000)
Fiscal Year 2012: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
Keywordsパラジウム / 多核錯体 / ゲルミレン配位子 / プロトン化 / 平面錯体 / 転位反応 / シリル錯体 / ゲルミル錯体 / 白金錯体
Outline of Final Research Achievements

Protonation was studied for the tetrapalladium complexes and triplatinum complexes with bridging germylene ligands. The reaction is influenced by the protic acid used, and protonation by weak organic acid causes reversible protonation and deprotonation.
Use of trifluoroacetic acid as the proton source provided the complex having a hydride ligand for the tetrapalladium core, which is considered to be the important intermediate of the total reaction, which is accompanied by change of the molecular structure. Further reaction resulted in an octanuclear complex having two tetrapalladium cores with cleavage of an Pd-Si bond and bishosphine spacer betseen the Pd4 cores. Based on these results, the mechanism of the protonation and accompanying structural change is clarified.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (17 results)

All 2015 2014 2013 2012 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Acknowledgement Compliant: 1 results) Presentation (10 results) (of which Invited: 2 results) Remarks (1 results)

  • [Journal Article] Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Pd(I) Complexes2015

    • Author(s)
      Makoto Tanabe, Shumpei Omine, Naoko Ishikawa, Kohtaro Osakada, Yoshihiro Hayashi, Susumu Kawauchi
    • Journal Title

      Angewandte Cheme International Edition

      Volume: 54 Issue: 9 Pages: 2679-2683

    • DOI

      10.1002/anie.201411041

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Triangular Triplatinum(0) Complex with Bridging Germylene Ligands. Insertion of Alkyne into the Pt‒Ge Bond Rather Than the Pt‒Pt Bond2014

    • Author(s)
      Makoto Tanabe, Kimiya Tanaka, Shumpei Omine, Kohtaro Osakada
    • Journal Title

      Chemical Communications

      Volume: 50 Issue: 52 Pages: 6839-6842

    • DOI

      10.1039/c4cc00727a

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cationic Hydridotriplatinum Complex with Bridging Germylene Ligands2014

    • Author(s)
      Kimiya Tanaka, Makoto Tanabe, Tomohito Ide, Kohtaro Osakada
    • Journal Title

      Organometallics

      Volume: 33 Issue: 10 Pages: 2608-2612

    • DOI

      10.1021/om500309k

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ring-opening Reaction of a Pergermylated Platinacyclopentane Forming 1,4-Bis(arenethiolato)tetragermanes2012

    • Author(s)
      Makoto Tanabe, Takashi Deguchi, Kohtaro Osakada
    • Journal Title

      Organometallics

      Volume: 31(21) Issue: 21 Pages: 7386-7393

    • DOI

      10.1021/om300655m

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice2012

    • Author(s)
      Makoto Tanabe, Ryouhei Yumoto, Kohtaro Osakada, Takanobu Sanji, Masato Tanaka
    • Journal Title

      Organometallics

      Volume: 31(19) Issue: 19 Pages: 6787-6795

    • DOI

      10.1021/om300551t

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction of alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si-C and Si-Si bond-making processes2012

    • Author(s)
      田邊真, 湯本遼平, 小坂田耕太郎
    • Journal Title

      Chem. Commun

      Volume: 48 Issue: 15 Pages: 2125-2127

    • DOI

      10.1039/c2cc16063c

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] アルキン付加による橋架けシリレン-白金三核錯体の骨格変換反応2015

    • Author(s)
      鴨野 萌,田中 君弥,田邊 真, 小坂田 耕太郎
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Preparation of Cationic Triplatinum Complexes Stabilized by Bridging Germylene Ligands2015

    • Author(s)
      Kimiya Tanaka, Makoto Tanabe, Kohtaro Osakada
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Multinuclearization of Silylene-bridged Dipalladium Intermediates Leading to the Formation of Planar Tetrapalladium Complexes2015

    • Author(s)
      Hiroyuki Toi, Makoto Tanabe, Kohtaro Osakada
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] 橋架けシリレン-遷移金属二核錯体を用いる不飽和有機分子の活性化2015

    • Author(s)
      中村優、田邊真、小坂田耕太郎
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Triangular Triplatinum Complexes with Bridging Germylene Ligands and Their Protonation on the Pt3 Core2014

    • Author(s)
      Kimiya Tanaka, Makoto Tanabe, Kohtaro Osakada
    • Organizer
      9th Workshop on Organic Chemistry
    • Place of Presentation
      東京工業大学すずかけ台キャンパス(神奈川県・横浜市)
    • Year and Date
      2014-11-07 – 2014-11-10
    • Related Report
      2014 Annual Research Report
  • [Presentation] 橋架けケイ素配位子が作る新しい有機金属錯体の世界2014

    • Author(s)
      小坂田耕太郎
    • Organizer
      第18回ケイ素化学協会シンポジウム
    • Place of Presentation
      ラフォーレ那須(栃木県・那須郡)
    • Year and Date
      2014-10-17 – 2014-10-18
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Protonation of the Triangular Pt3Ge3 Complexes2014

    • Author(s)
      Makoto TANABE, Kimiya TANAKA, Tomohito IDE, Kohtaro OSAKADA
    • Organizer
      XXVIth International Conference of Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌(北海道・札幌市)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] 高周期14族元素により安定化された白金多核錯体の合成と反応2013

    • Author(s)
      田中 君弥, 大嶺 俊平, 田邊 真, 小坂田 耕太郎
    • Organizer
      錯体化学第63回討論会
    • Place of Presentation
      沖縄
    • Related Report
      2013 Annual Research Report
  • [Presentation] 有機シリレン反応剤を利用する平面構造遷移金属多核錯体の構築2013

    • Author(s)
      遠井 宏幸, 湯本 遼平, 酒井 優, 田邊 真, 小坂田 耕太郎
    • Organizer
      第60回有機金属化学討論会
    • Place of Presentation
      東京
    • Related Report
      2013 Annual Research Report
  • [Presentation] 有機ケイ素配位子をもつ遷移金属錯体の新構造と新反応2013

    • Author(s)
      小坂田耕太郎
    • Organizer
      第46回有機金属化学夏の学校
    • Place of Presentation
      仙台
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Remarks] 小坂田竹内研究室最近の論文

    • URL

      http://www.res.titech.ac.jp/~shinkin/paper.html#y2015

    • Related Report
      2014 Annual Research Report

URL: 

Published: 2012-04-24   Modified: 2019-07-29  

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