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

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

  • Jurt P Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Salnikov OG International Tomography Center , SB RAS , Novosibirsk , Russia.
  • Gianetti TL Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Chukanov NV International Tomography Center , SB RAS , Novosibirsk , Russia.
  • Baker MG Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Le Corre G Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Borger JE Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Verel R Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Gauthier S Université de Rennes , CNRS , ISCR-UMR 6226 , F-35000 Rennes , France.
  • Fuhr O Institute of Nanotechnology , Karlsruhe Institute of Technology (KIT) , Eggenstein-Leopoldshafen , Germany.
  • Kovtunov KV International Tomography Center , SB RAS , Novosibirsk , Russia.
  • Fedorov A Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
  • Fenske D Institute of Nanotechnology , Karlsruhe Institute of Technology (KIT) , Eggenstein-Leopoldshafen , Germany.
  • Koptyug IV International Tomography Center , SB RAS , Novosibirsk , Russia.
  • Grützmacher H Department of Chemistry and Applied Biosciences , ETH Zürich , Switzerland . Email: hgruetzmacher@ethz.ch.
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  • 2019-11-02
Published in:
  • Chemical science. - 2019
General Chemistry
English 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 C[triple bond, length as m-dash]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 H2 activation by interfacial sites of heterogeneous Rh/C catalysts.
Language
  • English
Open access status
gold
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Persistent URL
https://sonar.ch/global/documents/79059
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