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Journal articles
Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates
Pascal Jurt
1
Oleg G. Salnikov
2, 3
Thomas L. Gianetti
4, *
Nikita V. Chukanov
2, 3
Matthew G. Baker
1
Gregoire Le Corre
1
Jaap E. Borger
1
Rene Verel
1
Sebastien Gauthier
5
Olaf Fuhr
6
Kirill V. Kovtunov
2, 3
Alexey Fedorov
1
Dieter Fenske
6
Igor V. Koptyug
2
Hansjorg Grutzmacher
1, *
*
Corresponding author
Pascal Jurt 1
Author
Oleg G. Salnikov 2, 3
Author
Thomas L. Gianetti 4
Correspondent author
Nikita V. Chukanov 2, 3
Author
Sebastien Gauthier 5
Author
Olaf Fuhr 6
Author
Kirill V. Kovtunov 2, 3
Author
Alexey Fedorov 1
Author
1
ETH Zürich - Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (Hauptgebäude, Rämistrasse 101, 8092 Zürich - Switzerland)
2
RAS - Russian Academy of Sciences [Moscow] (Leninsky Ave, 14, Moscow, Russie, 119991 - Russia)
3
NSU - Novosibirsk State University (Pirogova str. 2, 630090 Novosibirsk - Russia)
4
University of Arizona (Tucson AZ 85721 USA - United States)
5
ISCR - Institut des Sciences Chimiques de Rennes (Campus de Beaulieu - Bât. 10 Avenue du Général Leclerc 35042 Rennes Cedex - France)
- ENSCR - Ecole Nationale Supérieure de Chimie de Rennes (France)
- UR1 - Université de Rennes 1 (2 rue du Thabor - CS 46510 - 35065 Rennes cedex - France)
- UNIV-RENNES - Université de Rennes (France)
- INSA Rennes - Institut National des Sciences Appliquées - Rennes (20, avenue des Buttes de Coësmes - CS 70839 - 35708 Rennes cedex 7 - France)
- CNRS - Centre National de la Recherche Scientifique : UMR6226 (France)
6
KIT - Karlsruhe Institute of Technology (Campus North, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen / Campus South, Kaiserstraße 12, 76131 Karlsruhe - Germany)
Abstract : Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two C and xe002;C bonds of the trop ligand. This reaction is chemoselective and converts C and xe002;C bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H-2 activation by interfacial sites of heterogeneous Rh/C catalysts.
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Journal articles
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-02303398
Contributor : Catherine Derennes <>
Submitted on : Wednesday, April 1, 2020 - 5:20:39 PM
Last modification on : Thursday, May 27, 2021 - 1:54:06 PM
Contributor : Catherine Derennes <>
Submitted on : Wednesday, April 1, 2020 - 5:20:39 PM
Last modification on : Thursday, May 27, 2021 - 1:54:06 PM
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c9sc02683e.pdf;
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Identifiers
- HAL Id : hal-02303398, version 1
- DOI : 10.1039/c9sc02683e
- PUBMED : 31673319
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UNIV-RENNES1 | UNIV-RENNES | UR1-UFR-SPM | ISCR-OMC | ISCR | INC-CNRS | CNRS | INSA-GROUPE | INSA-RENNES
Citation
Pascal Jurt, Oleg G. Salnikov, Thomas L. Gianetti, Nikita V. Chukanov, Matthew G. Baker, et al.. Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates. Chemical Science , The Royal Society of Chemistry, 2019, 10 (34), pp.7937-7945. ⟨10.1039/c9sc02683e⟩. ⟨hal-02303398⟩
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