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An Efficient Methyltrioxorhenium(VII)-Catalyzed Transformation of Hydrotrioxides (ROOOH) into Dihydrogen Trioxide (HOOOH)

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Department of Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, P.O. Box 537, 1000 Ljubljana, Slovenia, and WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, U.K.
†University of Ljubljana.
‡University of Strathclyde.
Cite this: J. Am. Chem. Soc. 2008, 130, 43, 14086–14087
Publication Date (Web):October 4, 2008
https://doi.org/10.1021/ja806411a
Copyright © 2008 American Chemical Society

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    Abstract

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    Dihydrogen trioxide (HOOOH) is formed nearly quantitatively in the low-temperature (−70 °C) methyltrioxorhenium(VII) (MTO)-catalyzed transformation of silyl hydrotrioxides (R3SiOOOH), and some acetal hydrotrioxides, in various solvents, as confirmed by 1H, and 17O NMR spectroscopy. The calculated energetics (B3LYP) for the catalytic cycle, using H3SiOOOH as a model system, is consistent with the experimentally observed activation energy (9.5 ± 2.0 kcal/mol) and a small kinetic solvent isotope effect (kH2O/kD2O = 1.1 ± 0.1), indicating an initial concerted reaction between the silyl hydrotrioxide and MTO in the rate-determining step. With the addition of water in the next step, the intermediate undergoes a σ-bond metathesis reaction to break the Re-OOOH bond and form HOOOH, together with the second dihydroxy intermediate. The final step in the catalytic cycle involves a second, catalytic water that lowers the barrier to form H3SiOH and MTO.

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    Complete ref 10; additional experimental and computational details, NMR spectra, figure and tables of kinetic data, the structures, Cartesian coordinates and energetic data of all species indicated in the text are provided. This material is available free of charge via the Internet at http://pubs.acs.org.

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    1. Janez Cerkovnik and Božo Plesničar . Recent Advances in the Chemistry of Hydrogen Trioxide (HOOOH). Chemical Reviews 2013, 113 (10) , 7930-7951. https://doi.org/10.1021/cr300512s
    2. Siwei Bi, Jiayong Wang, Lingjun Liu, Ping Li, and Zhenyang Lin . Mechanism of the MeReO3-Catalyzed Deoxygenation of Epoxides. Organometallics 2012, 31 (17) , 6139-6147. https://doi.org/10.1021/om300485w
    3. Tell Tuttle, Janez Cerkovnik, Jože Koller and Božo Plesničar. The Search for Protonated Dihydrogen Trioxide (HOOOH): Insights from Theory and Experiment. The Journal of Physical Chemistry A 2010, 114 (30) , 8003-8008. https://doi.org/10.1021/jp103882e
    4. Mustafa Catir, Hamdullah Kilic, Véronique Nardello-Rataj, Jean-Marie Aubry and Cavit Kazaz . Singlet Oxygen Generation from [Bis(trifluoroacetoxy)iodo]benzene and Hydrogen Peroxide. The Journal of Organic Chemistry 2009, 74 (12) , 4560-4564. https://doi.org/10.1021/jo9007496
    5. D. Veljanovski. peroxidation. 2020https://doi.org/10.1002/9783527809080.cataz12616
    6. R.W. Fischer. methyltrioxorhenium. 2020https://doi.org/10.1002/9783527809080.cataz10662
    7. Gérard Audran, Sylvain R.A. Marque, Maurice Santelli. Ozone, chemical reactivity and biological functions. Tetrahedron 2018, 74 (43) , 6221-6261. https://doi.org/10.1016/j.tet.2018.09.023
    8. Lennart Brütsch, Claus Feldmann. Synthesis and Morphology of AgReO 4 Plates, Rods, and Stars. Zeitschrift für anorganische und allgemeine Chemie 2017, 643 (12) , 789-792. https://doi.org/10.1002/zaac.201700072
    9. A. V. Levanov, O. Ya. Isaikina, V. V. Lunin. Enthalpies of the formation and decomposition of hydrogen trioxide HOOOH in an aqueous solution. Russian Journal of Physical Chemistry A 2016, 90 (11) , 2136-2141. https://doi.org/10.1134/S0036024416110145
    10. Gregor Strle, Janez Cerkovnik. A Simple and Efficient Preparation of High‐Purity Hydrogen Trioxide (HOOOH). Angewandte Chemie International Edition 2015, 54 (34) , 9917-9920. https://doi.org/10.1002/anie.201504084
    11. Gregor Strle, Janez Cerkovnik. A Simple and Efficient Preparation of High‐Purity Hydrogen Trioxide (HOOOH). Angewandte Chemie 2015, 127 (34) , 10055-10058. https://doi.org/10.1002/ange.201504084
    12. Alexander V. Levanov, Oksana Ya. Isaykina, Ewald E. Antipenko, Valerii V. Lunin. Hydrogen polyoxides H2O3 and H2O4 as components of peroxy radical condensate obtained from electro-dissociated water vapor. Chemical Physics 2015, 447 , 10-14. https://doi.org/10.1016/j.chemphys.2014.11.020
    13. Sergey L. Khursan. Peroxide intermediates of oxidation processes: Organic trioxides. 2014, 1-72. https://doi.org/10.1002/9780470682531.pat0874
    14. Andrew Hudson, Daniel Betz, Fritz E. Kühn, Guillermo H. Jiménez-Alemán, Wilhelm Boland. Methyltrioxorhenium. 2013https://doi.org/10.1002/047084289X.rn00017.pub3
    15. Daniel Cannon, Tell Tuttle, Jože Koller, Božo Plesničar. Stabilization of metastable hydrogen trioxide (HOOOH) and the hydrotrioxyl radical (HOOO) by complexation with sulfuric acid. A theoretical study. Computational and Theoretical Chemistry 2013, 1010 , 19-24. https://doi.org/10.1016/j.comptc.2013.01.009
    16. Tse‐Lok Ho, Mary Fieser, Louis Fieser. Methyltrioxorhenium( VII ). 2011, 371-372. https://doi.org/10.1002/9780471264194.fos07268.pub4
    17. Tse‐Lok Ho, Mary Fieser, Louis Fieser. Methyltrioxorhenium( VII ). 2011, 371-372. https://doi.org/10.1002/9780471264194.fos07268.pub3
    18. Andrew Hudson, Daniel Betz, Fritz E. Kühn. Methyltrioxorhenium. 2010https://doi.org/10.1002/047084289X.rn00017.pub2

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