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; Grégoire Le Corre; Jaap E. Borger; Rene Verel; Sébastien Gauthier; Olaf Fuhr; Kirill V. Kovtunov; Alexey Fedorov; Dieter Fenske; Igor V. Koptyug; Hansjörg Grützmacher

doi:10.1039/C9SC02683E

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

Pascal Jurt,^a Oleg G. Salnikov,^bc Thomas L. Gianetti,

*^ad Nikita V. Chukanov,^bc Matthew G. Baker,^a Grégoire Le Corre,^a Jaap E. Borger,^a Rene Verel,

^a Sébastien Gauthier,^e Olaf Fuhr,

^g Kirill V. Kovtunov,

^bc Alexey Fedorov,

^af Dieter Fenske,^g Igor V. Koptyug

^bc and Hansjörg Grützmacher

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Applied Biosciences, ETH Zürich, Switzerland
E-mail: hgruetzmacher@ethz.ch

^b International Tomography Center, SB RAS, Novosibirsk, Russia

^c Novosibirsk State University, Novosibirsk, Russia

^d Department of Chemistry and Biochemistry, University of Arizona, Tucson, USA
E-mail: tgianetti@email.arizona.edu

^e Université de Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France

^f Department of Mechanical and Process Engineering, ETH Zürich, Switzerland

^g Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, 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 [triple bond, length as m-dash] C bonds of the trop ligand. This reaction is chemoselective and converts CC 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 H₂ activation by interfacial sites of heterogeneous Rh/C catalysts.

Chemical Science

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

Abstract

Supplementary files

Article information

Download Citation

Permissions

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

Social activity

Search articles by author

Spotlight

Advertisements