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Rhodium(iii) complexes containing C4-bound N-heterocyclic carbenes: synthesis, coordination chemistry, and catalytic activity in transfer hydrogenation

  • Yang, Liangru Department of Chemistry, University of Fribourg, Switzerland - School of Chemistry and Chemical Engineering, Henan University of Techology, P. R. China.
  • Krüger, Anneke Department of Chemistry, University of Fribourg, Switzerland
  • Neels, Antonia Institute of Microtechnology, University of Neuchâtel, Switzerland
  • Albrecht, Martin Department of Chemistry, University of Fribourg, Switzerland
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  • Organometallics. - 2008, vol. 27, no. 13, p. 3161–3171
English Direct metalation of C2-protected diimidozolium salts with RhCl₃ or [RhCl(cod)]₂ and KI afforded a series of new rhodium(III) complexes with abnormally C4-bound, cis-chelating NHC ligands. The complexes were isolated as dimetallic species containing two (μ²-I)₃-bridged rhodium(III) centers. In the presence of coordinating ligands such as CH₃CN, PPh₃, or dppe, the dimeric structure is readily cleaved and yields monometallic complexes. Crystallographic analysis of representative structures indicates a higher trans influence of abnormally C4-bound carbenes as compared to normal NHCs. The exceptionally strong donor ability of carbenes in such a C4 coordination mode increases the catalytic activity of the rhodium center and allows for efficient transfer hydrogenation of ketones in iPrOH/KOH.
Faculté des sciences et de médecine
Département de Chimie
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