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Oxidative homocoupling of arenes is a challenging but attractive method converting non-activated aromatics into biaryl compounds. Applications and mechanistic understanding of bimetallic nanocatalysts for arene C–H bond activation are lim-ited at present. In this study, we found that Pd-Ru bimetallic catalyst supported on Al2O3 showed remarkably high catalytic activity for the oxidative homocoupling of arenes owing to the synergistic effect between Pd and Ru. Structural analyses by high-angle annular dark-field scanning transmission electron microscopy with energy dispersive X-ray spectroscopy and X-ray absorption spectroscopy revealed that Pd nanoparticles were decorated by partially oxidized Ru clusters. Mechanistic studies indicated that the arene C–H bond cleavage was the rate-determining step and proceeded by concerted metalation deprotonation mechanism. It was proposed that the role of Ru is promoting the C–H activation step by generating electron deficient Pd sites, which was supported by DFT calculations. The Ru-decorated Pd nanoparticles showed large turnover numbers for simple arenes.

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  This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.4c05551.

Keyword: Bimetallic catalyst, Palladium, Ruthenium, C-H bond activation, Oxidative coupling, Arene, Biaryl

Date published: 2025-01-03

Publisher: American Chemical Society (ACS)

Journal:

• ACS Catalysis (ISSN: 21555435) vol. 15 issue. 1 p. 487-493

Funding:

• Japan Society for the Promotion of Science JP22K20554
• Japan Society for the Promotion of Science JP23H04874
• Japan Society for the Promotion of Science JP23K13602
• Japan Society for the Promotion of Science JP23K23131
• Tokyo Ohka Foundation for The Promotion of Science and Technology

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5245

First published URL: https://doi.org/10.1021/acscatal.4c05551

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Updated at: 2025-01-06 16:26:31 +0900

Published on MDR: 2025-12-19 14:11:42 +0900