Unprecedented C-H Bond Functionalization by Design of Metal Nanoparticle-Metal Oxide Cluster Composite Catalysts

2022 Fiscal Year Final Research Report

• Project/Area Number: 21K14460
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 27030:Catalyst and resource chemical process-related
• Research Institution: The University of Tokyo
• Principal Investigator: Yatabe Takafumi 東京大学, 大学院工学系研究科(工学部), 助教 (60875532)
• Project Period (FY): 2021-04-01 – 2023-03-31
• Keywords: ナノ粒子 / 酸化物クラスター / C-H結合活性化 / 協奏的触媒作用 / DFT計算 / 酸化的脱水素 / 吸着制御 / 脱カルボニル

Outline of Final Research Achievements

Supported palladium nanooxide-on-gold nanoparticle catalysts were found to be much more active than homogeneous catalysts for C-H bond activation of saturated ketones. A combination of detailed characterization and quantum chemical calculations revealed that the key to achieve the reaction was the concerted activation by the unique Lewis acid-Bronsted base pair at the nanooxide-nanoparticle interface. In addition, the concerted catalysis and adsorption control by supported magnesium hydroxide-on-palladium nanoparticle catalysts enabled the selective synthesis of primary anilines with ammonia as the nitrogen source via acceptorless dehydrogenative aromatization, which has not been achieved without photo-irradiation. Furthermore, by applying the insight on the interaction between oxides and nanoparticles, we succeeded in the selective decarbonylation of aldehydes, 1,2-diketones, and thioesters.

Free Research Field

触媒化学、有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究では、ナノ酸化物-酸化物クラスター複合触媒を設計し、他の触媒系では実現できない特有の活性点構造を構築し、協奏的触媒作用や吸着制御を利用した高効率なC-H結合活性化や選択的脱水素反応を達成した。詳細な実験的キャラクタリゼーションやDFT計算からその活性点構造や反応機構を明らかにしており、ナノ酸化物-酸化物クラスター複合触媒が新たなC-H結合活性化を可能にすることを実証できたため、学術的意義は大きい。また、空気中の酸素を酸化剤としたり、酸化剤を用いずに水素も同時に製造するような環境調和的な反応系で、入手容易かつ安価な基質から多数の有用化合物を合成することに成功しており、社会的意義も大きい。