Preparation of Arsenic-Containing Ligands and Development of Novel Catalytic Reactions

2019 Fiscal Year Final Research Report

• Project/Area Number: 17K05803
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: Tanabe Yoshiaki 東京大学, 大学院工学系研究科(工学部), 研究員 (20384737)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 光反応 / フェロセン / サマリウム / 水 / 酸化反応 / ホスフィン / アンモニア / 窒素固定

Outline of Final Research Achievements

Molybdenum-catalyzed conversion of molecular dinitrogen into ammonia under ambient reaction conditions has been achieved by using a proton source generated in situ from the ruthenium-catalyzed oxidation of water in combination with visible light and a photosensitizer. The preset reaction system is considered as a new model for the nitrogen fixation by photosynthetic bacteria.
In addition, stoichiometric oxidation of phosphines with water and ferrocenium(III) cation as the oxygen atom source and the oxidizing reagent, respectively, was achieved in acetonitrile under visible-light irradiation by using 2,6-lutidine as the proton acceptor. The reaction required light irradiation, under which fluorescence was observed for the acetonitrile solution of the ferrocenium(III) cation.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

水をアンモニア生成反応のプロトン源として触媒的に使う道筋を初めて示した。またフェロセニウムカチオンが水の酸化剤として働くことによりフェロセンが生成するが、フェロセンに代表されるメタロセンは、窒素をアンモニアへと還元する反応の還元剤として働くことが知られており、本研究成果は窒素をアンモニアへと変換する触媒反応構築のための重要な進捗の一つといえる。