@article{oai:ynu.repo.nii.ac.jp:02001048,
 author = {Hasegawa, Shingo and Harano, Koji and Motokura, Ken},
 issue = {28},
 journal = {Journal of the American Chemical Society},
 month = {Jun},
 note = {Noble-metal-based bimetallic oxide clusters are promising novel catalysts. In this study, we developed carbon-supported RhRu bimetallic oxide clusters (RhRuOx/C) with a mean diameter of 1.2 nm, which showed remarkable catalytic activity for the cross-dehydrogenative coupling (CDC) of arenes and carboxylic acids with O2 as the sole oxidant. RhRu bimetallic oxide cluster formation was confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and synchrotron X-ray absorption spectroscopy. Kinetic isotope and substituent effects indicated that arene C–H bond cleavage was the rate-determining step and proceeded via electrophilic concerted metalation–deprotonation mechanism, with a carboxylate as an internal base. Density functional theory calculations supported the proposed mechanism and indicated that the active center for C–H bond activation was Rh(V) rather than Rh(III), while Ru enhanced the electrophilicity of the Rh(V) site by decreasing the negative charge of the surrounding oxygen atoms. Electron-rich arenes showed relatively high reactivity for the RhRuOx/C-catalyzed CDC reaction, and both aliphatic and aromatic carboxylic acids were applicable to the reaction. The RhRuOx/C catalyst is promising for the CDC reaction of arenes and carboxylic acids to produce aryl esters. This work promotes the development of noble-metal-based bimetallic oxide clusters for C–H bond activation reactions.},
 pages = {19059--19069},
 title = {RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling of Arenes and Carboxylic Acids},
 volume = {146},
 year = {2024}
}