Mechanistic Understanding of the Heterogeneous, Rhodium-Cyclic (Alkyl)(Amino)Carbene-Catalyzed (Fluoro-)Arene Hydrogenation.


Journal

ACS catalysis
ISSN: 2155-5435
Titre abrégé: ACS Catal
Pays: United States
ID NLM: 101562209

Informations de publication

Date de publication:
05 Jun 2020
Historique:
received: 04 03 2020
revised: 04 05 2020
entrez: 20 6 2020
pubmed: 20 6 2020
medline: 20 6 2020
Statut: ppublish

Résumé

Recently, chemoselective methods for the hydrogenation of fluorinated, silylated, and borylated arenes have been developed providing direct access to previously unattainable, valuable products. Herein, a comprehensive study on the employed rhodium-cyclic (alkyl)(amino)carbene (CAAC) catalyst precursor is disclosed. Mechanistic experiments, kinetic studies, and surface-spectroscopic methods revealed supported rhodium(0) nanoparticles (NP) as the active catalytic species. Further studies suggest that CAAC-derived modifiers play a key role in determining the chemoselectivity of the hydrogenation of fluorinated arenes, thus offering an avenue for further tuning of the catalytic properties.

Identifiants

pubmed: 32551183
doi: 10.1021/acscatal.0c01074
pmc: PMC7295364
doi:

Types de publication

Journal Article

Langues

eng

Pagination

6309-6317

Informations de copyright

Copyright © 2020 American Chemical Society.

Déclaration de conflit d'intérêts

The authors declare the following competing financial interest(s): The authors declare no conflict of interest. However, please, note that we patented the Process for Synthesizing Fluorinated Cyclic Aliphatic Compounds employing the investigated catalyst system: PCT/EP2018/054554.

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Auteurs

Daniel Moock (D)

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

Mario P Wiesenfeldt (MP)

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

Matthias Freitag (M)

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

Satoshi Muratsugu (S)

Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Aichi, Japan.

Satoru Ikemoto (S)

Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Aichi, Japan.

Robert Knitsch (R)

Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149 Münster, Germany.

Jacob Schneidewind (J)

Leibniz-Institut für Katalyse e. V., Albert-Einstein-Strasse 29a, 18059 Rostock, Germany.

Wolfgang Baumann (W)

Leibniz-Institut für Katalyse e. V., Albert-Einstein-Strasse 29a, 18059 Rostock, Germany.

Andreas H Schäfer (AH)

nanoAnalytics GmbH, Heisenbergstrasse 11, 48149 Münster, Germany.

Alexander Timmer (A)

nanoAnalytics GmbH, Heisenbergstrasse 11, 48149 Münster, Germany.

Mizuki Tada (M)

Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Aichi, Japan.
Research Center for Materials Science (RCMS) and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Aichi, Japan.

Michael Ryan Hansen (MR)

Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149 Münster, Germany.

Frank Glorius (F)

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

Classifications MeSH