The "peroxo perrhenic acid" H4Re2O 13: An oxygen-rich metal peroxide and oxidation catalyst

Wolfgang A. Herrmann, João D.G. Correia, Fritz E. Kühn, Georg R.J. Artus, Carlos C. Romão

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The rhenium oxides Re2O7 and ReO3 react with hydrogen peroxide solutions yielding peroxo complexes that efficiently catalyze the oxidation of olefins, aromatics, and certain organometallic compounds. In contrast, related oxides of molybdenum (MoO3) and vanadium (V2O5) do not activate H2O2 under comparable conditions. The active rhenium peroxo complex was isolated from the system Re2O7/H2O2: the crystalline red-or-ange, explosive compound of formula H4Re 2O13 is the most oxygen rich rhenium compound isolated to date. Its structure resembles a "peroxo perrhenic acid". The binuclear compound could be isolated in the form of a diglyme adduct, structurally defined as two corner-sharing pentagonal bipyramids with apical oxo and aquo ligands; the equatorial positions are occupied by the bridging oxygen and by λ2-peroxo groups (two [O2]2- ligands per rhenium). In contrast to the known complex [CH3ReO(O 2)2] · H2O, the new peroxo species [O{ReO(O2)2 H2O)2] decomposes hydrolytically during the catalytic cycle and can thus not compete in terms of catalytic activity in oxidation reactions involving H2O2. Hydrolysis yields "perrhenic acid" Re2O7· 2 H2O, the diglyme adduct of which compound was also characterized by means of an X-ray diffraction analysis.

Original languageEnglish
Pages (from-to)168-173
Number of pages6
JournalChemistry - A European Journal
Issue number2
StatePublished - 1996


  • Catalysis
  • Crystal structure
  • Oxidations
  • Rhenium peroxo complexes


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