Dioxygen Activation by a Low-Valent Meal-Oxo Complex as a Key Species

• Project/Area Number: 15K05462
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Institute for Molecular Science
• Principal Investigator: Kurahashi Takuya 分子科学研究所, 生命・錯体分子科学研究領域, 助教 (90353432)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 酸素分子の活性化 / 空気酸化 / 酸化還元電位 / 電子移動 / アニオンラジカル / サレンマンガン錯体 / ジオキソ架橋２核マンガン錯体 / サレン / マンガン / 二相反応 / ファインバブル / 光反応 / 酸素分子活性化 / 蛍光特性 / サレン錯体

Outline of Final Research Achievements

Catalytic oxygenation reactions require stoichiometric chemical oxidants for substrates. But the use of chemical oxidants accompanies undesired byproducts, which causes problems from the cost and environment viewpoints. The present study proposes and examines a new air oxygenation scheme using aqueous alkaline solution as a trigger. The present study shows that the reaction of a manganese(III) complex with aqueous alkaline solution gave a highly reducing species, leading to the activation of dioxygen in air.

Research Products

• [Journal Article] Drastic Redox Shift and Electronic Structural Changes of a Manganese(III)-Salen Oxidation Catalyst upon Reaction with Hydroxide and Cyanide Ion (2018)
  • Author(s): Kurahashi Takuya
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 3 Pages: 1066-1078
  • DOI: 10.1021/acs.inorgchem.7b02474
  • Peer Reviewed
• [Journal Article] Reverse Catalase Reaction: Dioxygen Activation via Two-Electron Transfer from Hydroxide to Dioxygen Mediated By a Manganese(III) Salen Complex (2015)
  • Author(s): Takuya Kurahashi
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 17 Pages: 8356-8366
  • DOI: 10.1021/acs.inorgchem.5b01025
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Rational Molecular Design of a Photoactive Salen Ligand (2017)
  • Author(s): Takuya Kurahashi
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 神奈川県横浜市（慶應義塾大学）
  • Year and Date: 2017-03-16
• [Presentation] Tautomerization of a Salen Ligand as a Key Factor for Enhanced Fluorescence Emission Efficiency (2017)
  • Author(s): Takuya Kurahashi
  • Organizer: 錯体化学会第６７回討論会
• [Presentation] 光触媒開発を目的とした光感応性サレン配位子の研究 (2017)
  • Author(s): 倉橋拓也
  • Organizer: 第５０回酸化反応討論会
• [Presentation] Anion Radical Character of a Six-Coordinate Manganese(III) Salen Complex: Implications for the Spectroscopy and Electronic Structure of Manganese Superoxide Dismutase (2016)
  • Author(s): Takuya Kurahashi
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡県福岡市（福岡大学）
  • Year and Date: 2016-09-10
• [Presentation] Dioxygen Activation via Two-Electron Transfer from Hydroxide to Dioxygen Mediated by a Manganese(III) Salen Complex (2016)
  • Author(s): Takuya Kurahashi
  • Organizer: 42th International Conference on Coordination Chemistry
  • Place of Presentation: Brest, France (Le Quartz congres)
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Presentation] High-valent manganese and cobalt complexes with redox-active salen ligands related to asymmetric catalysis (2015)
  • Author(s): Takuya Kurahashi
  • Organizer: Pacifichem 2015
  • Place of Presentation: 米国ハワイ州（ヒルトンハワイアンビレッジ）
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] 水酸化物イオンとの反応で生成するマンガン化学種と酸素分子の活性化 (2015)
  • Author(s): 倉橋 拓也
  • Organizer: 第４８回酸化反応討論会
  • Place of Presentation: 京都府京都市（同志社大学）
  • Year and Date: 2015-10-23
• [Presentation] Unique Spectroscopic and Redox Properties of a Manganese(III)-Hydroxide Complex with a Salen Ligand (2015)
  • Author(s): Takuya Kurahashi
  • Organizer: 錯体化学会第６５回討論会
  • Place of Presentation: 奈良県奈良市（奈良女子大学）
  • Year and Date: 2015-09-21
• [Presentation] Hydroxide-Promoted Dioxygen Activation by a Manganese(III) Salen Complex (2015)
  • Author(s): Takuya Kurahashi
  • Organizer: Metals in Biology in Wako
  • Place of Presentation: 埼玉県和光市（理研）
  • Year and Date: 2015-06-16
  • Int'l Joint Research
• [Book] "Unique Electronic and Stereochemical Properties of Salen Complexes" in "Conjugated Objects: Developments, Synthesis, and Applications" (2017)
  • Author(s): Takuya Kurahashi
  • Total Pages: 21
  • Publisher: Pan Stanford Publishing Pte. Ltd.