Activation of inert multiple bonds by low-valent multinuclear iron complexes

2018 Fiscal Year Final Research Report

• Project/Area Number: 16K05720
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka University
• Principal Investigator: Hatanaka Tsubasa 大阪大学, 理学研究科, 助教 (80595330)
• Research Collaborator: NAGATA Kojiro ; KUSUMOTO Masaaki ; WADA Musashi ; KAJITA Motoki ; KAWAHARA Kazuya ; MASUDA Hiroyuki ; YAMADA Yuka ; ASANO Kyohei ; ADACHI Miwako ; KUROKI Taito ; SHIMIZU Naoya ; WADA Chihiro ; ARAI Takuya ; KUSUNOSE Hinano
• Project Period (FY): 2016-04-01 – 2019-03-31
• Keywords: 鉄 / 基質活性化 / 多核錯体 / 結合切断反応 / 低原子価

Outline of Final Research Achievements

In order to achieve cleavage of inert multiple bonds by iron complexes, we examined synthesis of low-valent multinuclear iron complexes with highly electron-donating ligands, and performed multi-electron reduction of substrates with the complexes. When we used bidentate and tridentate amido ligands containing multiple aromatic rings, we were able to synthesize mono- to　tetranuclear complexes of low-valent iron, selectively, depending on the bulkiness of the ligands. In addition, the dinuclear complex was found to cleave the N = N double bond in azobenzene. When we used bisamido ligands with vanadocene moieties in the ligand skeleton, activation of the dinitrogen molecule was achieved with an iron complex having the ligand, and the complex containing two-electron-reduced dinitrogen was isolated.

Free Research Field

錯体化学

Academic Significance and Societal Importance of the Research Achievements

本研究の成果として低原子価多核錯体を用いた基質活性化を達成している。またその各段階の化学種を、種々の分光学的手法や単結晶X線構造解析によって同定しているため、多核金属クラスター上で小分子がどのように活性化されるかを詳細に考察することが可能である。これらの知見は、同様の反応を行ってはいるものの通常観測が非常に困難な、化学工業での固体触媒を用いた反応や生体内酵素活性中心の金属クラスターが行う反応の機構について理解するのに役立つ。