Precise Control of Dioxygen Activation by Copper Complexes and Application

2020 Fiscal Year Final Research Report

• Project/Area Number: 17H03031
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka University
• Principal Investigator: Itoh Shinobu 大阪大学, 工学研究科, 教授 (30184659)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 銅錯体 / 酸素の活性化 / 活性酸素錯体 / 酸化反応 / 反応性制御 / 反応機構

Outline of Final Research Achievements

In this study, we have investigated copper-oxygen chemistry systematically by using a variety of supporting ligands in order to accompulish 'precise controlling of dioxygen activation by copper complexes'. The results obtained in this research are as follows.
(1) The reaction control mechanism of copper-oxygen complexes have been elucidated by using an N3- tridentate ligands and N4-tetradentate ligands having a cyclic diamine skeleton. (2) Novel copper complexes having a tetrahedral geometry have been synthesized using a newly designed N3-tridentate ligand and their structure, physiochemical properties, and reactivity have been evaluated to get deeper insights into the role of ligand structures. (3) The structural control mechanism of a copper-active oxygen complex was clarified by employing a tripod-type tetradentate ligand with a bulky substituents. (4) We achieved the ligand design aiming at the creation of a novel mononuclear copper active centers of the copper monooxygenases.

Free Research Field

錯体化学、触媒化学、生物無機化学

Academic Significance and Societal Importance of the Research Achievements

銅錯体による酸素の活性化は、銅含有酸化酵素や、銅を触媒とする様々な有機合成反応における重要なプロセスであり、錯体化学、生物無機化学、触媒化学、有機合成化学などの広い分野で活発に研究が展開されてきた。各銅－活性酸素錯体の構造、物理化学的特性、反応性などについては生物無機化学や錯体化学の分野で活発に検討が加えられてきたが、それらの生成制御機構に関しては系統的な検討が殆ど成されてきておらず、不明な点が多く残されている。本研究では、様々な配位子を用いて銅－活性酸素錯体の生成機構の解明や反応性の制御を達成するものであり、酵素機能の解明や新しい酸化触媒の開発に繋がるものとしてその意義は大きい。