Synthesis of dinuclear iron complex with dioxygen activation ability

2021 Fiscal Year Final Research Report

• Project/Area Number: 18K05142
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 34010:Inorganic/coordination chemistry-related
• Research Institution: Kanazawa University
• Principal Investigator: Furutachi Hideki 金沢大学, 物質化学系, 准教授 (40332663)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Keywords: 二核鉄ペルオキソ錯体 / 酸素分子活性化 / C-H結合酸化 / 機能モデル / 反応中間体 / 酸化反応

Outline of Final Research Achievements

Dinuclear nonheme iron enzymes such as soluble methane monooxygenase (sMMO) and toluene monooxygenases (TMO) are responsible for C-H bond oxidation. In catalytic cycles of these enzymes, (peroxo)diiron(III) intermediates have been spectroscopically characterized as key intermediates, which show electrophilic and nucleophilic reactivity. Several (peroxo)diiron(III) complexes have been synthesized as structural and spectroscopical models, however only a few functional models have been reported where the peroxodiiron(III) complexes show oxidation reactivity. In this study, (peroxo)diiron(III) complexes were synthesized and their oxidation ability towards external substrates were studied.

Free Research Field

生物無機化学

Academic Significance and Societal Importance of the Research Achievements

酸素分子を酸化剤として用いたアルカンやアレーン類の水酸化は現代化学で最も難しく重要な酸化反応のひとつである。メタンのメタノールへの水酸化やクメン法にかわるフェノールの合成は，世界でチャレンジすべき触媒反応１０（1993年時点）にリストアップされているが，生体系のメタンモノオキシゲナーセ（MMO: 2Fe, nCu）やトルエンモノオキシゲナーゼ（TMO: 2Fe）のように酸素分子を活性化し，有機基質を酸化できる物質の報告例はほとんどない。したがって本研究は，多くの研究者が関心を持つ研究課題であり，酸素分子を活性化能を有する物質を合成する意義は大きい。