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Construction of a Novel Reduction Catalytic System Using a Pt(II)/Pt(III) Redox Pair

Research Project

Project/Area Number 18K05158
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionRikkyo University

Principal Investigator

WADA Tohru  立教大学, 理学部, 教授 (30342637)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords白金錯体 / 酸化還元 / トリアザシクロノナン / 酸化還元反応 / 金属錯体 / 触媒
Outline of Final Research Achievements

We have prepared a Pt(IV) complex having a 1,4,7-triazacyclononane and revealed that two-electron reduction of the complex and oxidation reactions of the reduced form proceed via a different process. The isolated square-planar Pt(II) complex reacted with bromine or iodine to provide the corresponding Pt(IV) complex quantitatively. This reaction proceeds via electron transfer from Pt(II) complex to bromine or iodine followed by coordination of a halide ion to Pt(IV) complex. This research has successfully demonstrated that Pt complex, which is generally redox inert, become be active for redox reactions by introduction of 1,4,7-triazacyclononane.

Academic Significance and Societal Importance of the Research Achievements

Pt(II)錯体は四配位平面正方型、Pt(IV)錯体は六配位八面体型構造を好むため、Pt錯体の酸化還元には大きな構造変化を伴い、一般的に酸化還元不活性だと知られている。本研究では、環状三座配位子1,4,7-トリアザシクロノナンを導入することによって白金錯体が酸化還元活性になることを明らかにした。Pt(IV)からPt(II)への還元過程とPt(II)からPt(IV)への酸化過程は異なる経路で進行する。電子移動後に配位子の結合が進行する酸化過程を利用することで、ハロゲンーハロゲン結合の解離が可能になることを明らかにした。以上の結果から、白金錯体の酸化還元触媒としての新たな可能性を見出した。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (3 results)

All 2019 2018

All Presentation (3 results)

  • [Presentation] 配位子の脱着を伴った酸化還元挙動を示す1,4,7-トリアザシクロノナン-白金錯体の配位子効果の解明2019

    • Author(s)
      代順一郎、中薗孝志、和田亨
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Influence of ligand elimination on reversible stractural changes accompanying the two-electron redox reaction of Pt(tacn) (tacn = 1,4,7-triazacyclononane) complexes2019

    • Author(s)
      代順一朗、中薗孝志、和田亨
    • Organizer
      日本化学会 第99春季年会(2019)
    • Related Report
      2018 Research-status Report
  • [Presentation] 1,4,7-トリアザシクロノナン-白金錯体の酸化還元挙動に対する配位子効果の解明2018

    • Author(s)
      代順一朗、中薗孝志、和田亨
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Research-status Report

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Published: 2018-04-23   Modified: 2022-01-27  

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