Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Pascal Jurt; Oleg G. Salnikov; Thomas L. Gianetti; Nikita V. Chukanov; Matthew G. Baker; Gregoire Le Corre; Jaap E. Borger; Rene Verel; Sebastien Gauthier; Olaf Fuhr; Kirill V. Kovtunov; Alexey Fedorov; Dieter Fenske; Igor V. Koptyug; Hansjorg Grutzmacher

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

1 ETH Zürich - Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology in Zürich [Zürich]

2 RAS - Russian Academy of Sciences [Moscow]

3 NSU - Novosibirsk State University

4 University of Arizona

5 ISCR - Institut des Sciences Chimiques de Rennes

6 KIT - Karlsruhe Institute of Technology

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.

Document type :

Journal articles

Domain :

Chemical Sciences

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https://hal-univ-rennes1.archives-ouvertes.fr/hal-02303398
Contributor : Laurent Jonchère <>
Submitted on : Wednesday, October 2, 2019 - 11:52:10 AM
Last modification on : Tuesday, November 12, 2019 - 4:57:44 PM

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

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Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

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