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

doi:10.1002/chem.19960020208

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

Research output: Contribution to journal › Article › peer-review

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Abstract

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 language	English
Pages (from-to)	168-173
Number of pages	6
Journal	Chemistry - A European Journal
Volume	2
Issue number	2
DOIs	https://doi.org/10.1002/chem.19960020208
State	Published - 1996

Keywords

Catalysis
Crystal structure
Oxidations
Rhenium peroxo complexes

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title = "The {"}peroxo perrhenic acid{"} H4Re2O 13: An oxygen-rich metal peroxide and oxidation catalyst",

abstract = "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.",

keywords = "Catalysis, Crystal structure, Oxidations, Rhenium peroxo complexes",

author = "Herrmann, {Wolfgang A.} and Correia, {Jo{\~a}o D.G.} and K{\"u}hn, {Fritz E.} and Artus, {Georg R.J.} and Rom{\~a}o, {Carlos C.}",

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T1 - The "peroxo perrhenic acid" H4Re2O 13

T2 - An oxygen-rich metal peroxide and oxidation catalyst

AU - Herrmann, Wolfgang A.

AU - Correia, João D.G.

AU - Kühn, Fritz E.

AU - Artus, Georg R.J.

AU - Romão, Carlos C.

PY - 1996

Y1 - 1996

N2 - 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.

AB - 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.

KW - Catalysis

KW - Crystal structure

KW - Oxidations

KW - Rhenium peroxo complexes

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

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