Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

Authors
  • C. Tejel
  • M.A. Ciriano
  • M.P. del Río
  • F.J. van den Bruele
Publication date 2008
Journal Journal of the American Chemical Society
Volume | Issue number 130 | 18
Pages (from-to) 5844-5845
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
Abstract Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2 by O-2 leads to the mononuclear carboamido complex [Rh(nbd)(bpam-H)] (3) (bpam = N-(2-picolyl)picolinamide). The second () atom of O-2 ends up as a hydroxo fragment in [{Rh(nbd)(mu-OH))(2)].
Document type Article
Published at
https://doi.org/10.1021/ja711495v (Final published version)
Permalink to this page
Back