# RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling of Arenes and Carboxylic Acids

https://mdr.nims.go.jp/datasets/1d453c73-c69d-4cfc-b160-8f764a9c7ac6

## File

- [jacs_fin.pdf](https://mdr.nims.go.jp/filesets/7456f7cb-4eb7-449c-88b2-5120ecb80fb8/download) ([Detail](https://mdr.nims.go.jp/filesets/7456f7cb-4eb7-449c-88b2-5120ecb80fb8.md))

## Id

1d453c73-c69d-4cfc-b160-8f764a9c7ac6

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2024-08-09T07:38:32.038032Z

## Updated at

2025-06-05T23:30:18.875395Z

## Published at

2025-06-05T23:20:15.023934Z

## Doi

https://doi.org/10.48505/nims.4689

## First published url

https://doi.org/10.1021/jacs.4c03467

## Date published

2024-07-17

## Recorded date published

2024-7-17

## Resource type

journal_article

## Manuscript type

accepted_manuscript

## Collection



## Title

- title: RhRu Bimetallic Oxide Cluster Catalysts for Cross-Dehydrogenative Coupling
    of Arenes and Carboxylic Acids
  title_type: original
  lang: en

## Description

- description: '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 oxi-dant. 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 absorp-tion
    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 carbox-ylate 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 rela-tively
    high reactivity for 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 will promote the development of noble-metal-based bimetallic oxide clusters
    for C–H bond activation reactions. '
  description_type: abstract
  lang: und

## Creator

- name: Shingo Hasegawa
  role: author
- name: Koji Harano
  role: author
  orcid: https://orcid.org/0000-0001-6800-8023
  organization: National Institute for Materials Science
  ror: https://ror.org/026v1ze26
- name: Ken Motokura
  role: author

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: catalyst
  schema: not_defined
- subject: bimetallic nanoparticles
  schema: not_defined
- subject: scanning transmission electron microscopy
  schema: not_defined
- subject: cross-dehydrogenative coupling
  schema: not_defined

## Rights

- description: This document is the Accepted Manuscript version of a Published Work
    that appeared in final form in Journal of the American Chemical Society, 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/jacs.4c03467
  identifier: http://rightsstatements.org/vocab/InC/1.0/

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo

start_date: 2024-06-06
end_date: 2025-06-06

## Journal

- title: Journal of the American Chemical Society
  issn: '15205126'
  volume: '146'
  issue: '28'
  start_page: 19059
  end_page: 19069

## Conference



## Related item



## Funding

- identifier: JP22K20554
  funder_name: Japan Society for the Promotion of Science
- identifier: JP23H04874
  funder_name: Japan Society for the Promotion of Science
- identifier: JP23K13602
  funder_name: Japan Society for the Promotion of Science
- identifier: JP23K23131
  funder_name: Japan Society for the Promotion of Science
- funder_name: Tokyo Ohka Foundation for The Promotion of Science and Technology

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## Fileset

- id: 7456f7cb-4eb7-449c-88b2-5120ecb80fb8
  filename: jacs_fin.pdf
  content_type: application/pdf
  size: 15140447
  md5: 364213c4c2193d283918201f65b782a2

## Thumbnail

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filename: jacs_fin.pdf