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Synthesis of Mixed-Metal Metallocenoid Clusters

Research Project

Project/Area Number 23655051
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionInstitute for Molecular Science (2012)
Osaka University (2011)

Principal Investigator

MURAHASHI Tetsuro  分子科学研究所, 生命・錯体分子科学研究領域, 教授 (40314380)

Project Period (FY) 2011 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2012: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2011: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords金属錯体 / クラスター / 金属クラスター / サンドイッチ化合物 / パラジウム / 白金
Research Abstract

The mixed metal clusters have attracted great attention because a synergetic effect of different transition metal elements which are directly connected with each other via metal-metal bonds may give an advantage in physical properties or reactivity of metal clusters. Although much efforts have been made to incorporate different metals in a metal cluster framework, there remains a difficulty to attain a selective and efficient synthesis of tri- or higher nuclear mixed-metal clusters having a planned composition, in which the ligand environment around each metal is quasi-equivalent. The difficulty of controlling the metal stoichiometry, i.e., M_3, M_2M’, MM’_2, and M’_3, may arise not only from the thermodynamic but the kinetic factor : The incorporation rate of M to the triangular trimetal core is inherently different from that of M’, due to the different strength and reactivity of M-M, M-M’, and M’-M’ bonds. Furthermore, the ease of M-L and M’-L dissociation/association which might also be involved in the formation of trimetallic core can affect the selectivity of the mixed-metal core formations. Thus, a well-planned synthetic strategy is needed for the selective construction of M_2M’ and MM’_2 cores. In this project, we realized selective construction of the triangular PdPt_2 and Pd_2Pt cores in a common sandwich framework, where a key is to use different carbocyclic ligands for the different composite sandwich ; i.e., cycloheptatrienyl for PdPt_2, and cycloheptatriene for Pd_2Pt. After construction of the Pd_2Pt core, the cycloheptatriene ligands can be converted to cycloheptatrienyl ligands where a (carbocyclic ligand)-(metal triangle)-(carbocyclic ligand) sandwich structure was retained.

Report

(3 results)
  • 2012 Annual Research Report   Final Research Report ( PDF )
  • 2011 Research-status Report
  • Research Products

    (13 results)

All 2013 2012 2011 Other

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

  • [Journal Article] Selective Construction of Pd_2Pt and PdPt_2 Triangles in a Sandwich Framework : Carbocyclic Ligands as Scaffolds for a Mixed-Metal System2012

    • Author(s)
      T. Murahashi, K. Usui, Y. Tachibana, S. Kimura, S. Ogoshi
    • Journal Title

      Chem. Eur. J

      Volume: 18 Pages: 8886-8890

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Selective Construction of Pd2Pt and PdPt2 Triangles in a Sandwich Framework: Carbocyclic Ligands as Scaffolds for a Mixed-Metal System2012

    • Author(s)
      Tetsuro Murahashi
    • Journal Title

      Chemistry A European Journal

      Volume: 18 Issue: 29 Pages: 8886-8890

    • DOI

      10.1002/chem.201201474

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] 金属鎖および金属シートを持つサンドイッチ化合物の創製と性状解明2013

    • Author(s)
      村橋哲郎
    • Organizer
      東北大学卓越大学院研究会
    • Place of Presentation
      仙台
    • Year and Date
      2013-02-06
    • Related Report
      2012 Final Research Report
  • [Presentation] Chemistry of Dimensionally Extended Sandwich Compounds2012

    • Author(s)
      村橋哲郎
    • Organizer
      RIKEN International Symposium on Frontiers of Organometallic Chemistry
    • Place of Presentation
      埼玉
    • Year and Date
      2012-11-30
    • Related Report
      2012 Final Research Report
  • [Presentation] Synthesis and Structure of Metal Sheet Sandwich Complexes2012

    • Author(s)
      村橋哲郎
    • Organizer
      IKCOC-12
    • Place of Presentation
      京都
    • Year and Date
      2012-11-13
    • Related Report
      2012 Final Research Report
  • [Presentation] シクロヘプタトリエニル配位子を有するサンドイッチ型パラジウム―白金混合三核錯体の合成2012

    • Author(s)
      木村誠太、立花祐貴、臼井謙太郎、村橋哲郎、生越専介
    • Organizer
      日本化学会第92 春季年会
    • Place of Presentation
      東京
    • Year and Date
      2012-03-28
    • Related Report
      2012 Final Research Report
  • [Presentation] シクロヘプタトリエニル配位子を有するサンドイッチ型パラジウム―白金混合三核錯体の合成2012

    • Author(s)
      木村誠太・立花祐貴・臼井謙太郎・村橋哲郎・生越専介
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶應義塾大学
    • Related Report
      2011 Research-status Report
  • [Presentation] サンドイッチ化合物の構造次元性拡張2011

    • Author(s)
      村橋哲郎
    • Organizer
      名古屋大学GCOE シンポジウム
    • Place of Presentation
      名古屋
    • Year and Date
      2011-10-22
    • Related Report
      2012 Final Research Report
  • [Presentation] サンドイッチ化合物の構造次元性拡張2011

    • Author(s)
      村橋哲郎
    • Organizer
      名古屋大学GCOEシンポジウム(招待講演)
    • Place of Presentation
      名古屋大学
    • Related Report
      2011 Research-status Report
  • [Presentation] Synthesis and Structure of Metal Sheet Sandwich Complexes

    • Author(s)
      Tetsuro Murahashi
    • Organizer
      IKCOC-12
    • Place of Presentation
      京都府 リーガロイヤル京都ホテル
    • Related Report
      2012 Annual Research Report
  • [Presentation] Chemistry of Dimensionally Extended Sandwich Compounds

    • Author(s)
      Tetsuro Murahashi
    • Organizer
      RIKEN International Symposium on Frontiers of Organometallic Chemistry
    • Place of Presentation
      埼玉県 理化学研究所
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 金属鎖および金属シートを持つサンドイッチ化合物の創製と性状解明

    • Author(s)
      村橋哲郎
    • Organizer
      東北大学卓越大学院研究会「金属錯体の固体物性最前線―金属錯体と固体物性物理と生物物理の連携新領域を目指してー」
    • Place of Presentation
      宮城県 東北大学
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Remarks]

    • URL

      http://groups.ims.ac.jp/organization/murahashi_g/index.html

    • Related Report
      2012 Final Research Report

URL: 

Published: 2011-08-05   Modified: 2019-07-29  

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