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Development of new catalytic reactions over active sites on metal atoms of cluster complexes

Research Project

Project/Area Number 15K18267
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Catalyst/Resource chemical process
Research InstitutionSaitama University

Principal Investigator

NAGASHIMA Sayoko  埼玉大学, 理工学研究科, その他 (20442999)

Project Period (FY) 2016-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2017: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2016: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywords不均一系触媒 / クラスター錯体 / 無機材料 / 固体酸 / ルイス酸 / ブレンステッド酸 / レニウム / 触媒
Outline of Final Research Achievements

When a silica gel-supported rhenium sulfide cluster whose external ligand are hydroxo ligand is treated in a hydrogen stream in the temperature range 250-500 °C, catalytic activity for the Friedel-Crafts acylation reaction of anisole and benzoyl chloride develops. The catalytically active site of the cluster is a hydroxo ligand is an uncoordinated metal site (Lewis acid site) developed by the loss of a water molecule from two hydroxo ligands.
The activation mechanism of the rhenium sulfide clusters is expected to differ depending on the external ligand. The rhenium sulfide clusters having phenoxide ligands were obtained by the direct substitution of terminal chloride ligands by reaction with silver p-cyanophenolate and p-nitrophenolate. The structure of the clusters exhibits a quasiperfect octahedral Re6 cluster geometry, as shown by the similar values of the interatomic Re-Re distances as well as by Re-Re-Re angles close to 60° and 90°.

Academic Significance and Societal Importance of the Research Achievements

Friedel-Craftsアシル化は芳香族ケトンの工業的製造法として重要な反応の1つであるが、従来使用されている塩化アルミニウムを触媒として用いると化学両論量以上必要とする。クラスター錯体を触媒として用いることで不均一系での反応が可能となり、省エネルギー、低コスト化が期待できる。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (5 results)

All 2019 2018 2016

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Acknowledgement Compliant: 1 results) Presentation (2 results)

  • [Journal Article] Crystal structure of the octahedral rhenium cluster complex (Bu4N)4[Re6S8(OC6H4-p-NO2)6]2019

    • Author(s)
      Nagashima S, Kawada S, Kobayashi H.
    • Journal Title

      Journal of Structural Chemistry

      Volume: 60 Issue: 2 Pages: 299-301

    • DOI

      10.26902/jsc_id39233

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Application of solid-state early-transition metal clusters as catalysts2018

    • Author(s)
      Kamiguchi S, Nagashima S, Chihara T.
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Pages: 1337-1342

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of chromenes by cyclizative condensation of phenols with α,β-unsaturated carbonyl compounds over halide cluster catalysts2016

    • Author(s)
      Nagashima, Sayoko; Takahashi, Toru; Nasrin, Noor; Kamiguchi, Satoshi; Chihara, Teiji
    • Journal Title

      Chemistry Letters

      Volume: 45 Issue: 11 Pages: 1321-1323

    • DOI

      10.1246/cl.160681

    • NAID

      130005509482

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 窒素供与体配位子を有する八面体モリブデンクラスター錯体の合成2019

    • Author(s)
      本郷 倭、長島佐代子、栁瀬郁夫
    • Organizer
      第29回日本MRS年次大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] フェノキシド類を外部配位子にもつ新規レニウムスルフィドクラスター錯体の合成と構造2018

    • Author(s)
      川田壮志・長島佐代子・小林秀彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report

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Published: 2015-04-16   Modified: 2021-02-19  

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