- A Simple and Efficient Preparation of High-Purity Hydrogen Trioxide (HOOOH)
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A simple and efficient method allows the synthesis of solutions of high-purity hydrogen trioxide (HOOOH), released in the low-temperature methytrioxorhenium(VII) (MTO)-catalyzed transformation of the ozonized polystyrene-supported dimethylphenylsilane. High-purity hydrogen trioxide solutions in diethyl ether, separated from the polymer and free of any reactants and by-products, can be stored at -20°C for weeks. By removing the solvent in vacuo, HOOOH could be isolated in highly pure form or transferred to other solvents, thus significantly extending the research perspectives of HOOOH for novel applications.
- Strle, Gregor,Cerkovnik, Janez
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- The rotational spectrum and structure of HOOOH
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Dihydrogen trioxide, HOOOH, which is a species with fundamental importance for understanding the chain formation ability of the oxygen atom, was detected in a supersonic jet by a Fourier transform microwave spectrometer with a pulsed discharge nozzle, together with double resonance and triple resonance techniques. Its precise molecular structure was determined from the experimentally determined rotational constants of HOOOH and its isotopomer, DOOOD. Many of the microwave and millimeter wave transitions can now be accurately predicted, which could be facilitated for remote sensing of the molecule to elucidate its roles in various chemical processes. Copyright
- Suma, Kohsuke,Sumiyoshi, Yoshihiro,Endo, Yasuki
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- Dihydrogen trioxide (HOOOH) is generated during the thermal reaction between hydrogen peroxide and ozone
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Quantifiable amounts of HOOOH can be detected by 1H NMR spectroscopic analysis; of the thermal reaction of O3 and HOOH (see scheme). This first experimental report of a link between these three oxidants suggests that HOOOH may be involved in oxidation reactions that span biological, atmospheric, and environmental systems.
- Nyffeler, Paul T.,Boyle, Nicholas A.,Eltepu, Laxman,Wong, Chi-Huey,Eschenmoser, Albert,Lerner, Richard A.,Wentworth Jr., Paul
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- Enthalpies of the formation and decomposition of hydrogen trioxide HOOOH in an aqueous solution
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The enthalpies of the formation and decomposition of hydrogen trioxide are estimated from the heating curves of peroxide-radical condensates synthesized from gaseous O2 + H2 mixtures. Enthalpy of decomposition Н2О3(aq.) → Н2О(liq.) + О2(gas) is ?31.2 ± 1.5 kcal/mol, and enthalpy of formation ΔfH(H2O3, aq.) =–37.5 ± 1.6 kcal/mol. Both values correspond to the temperature range of 240–265 K.
- Levanov,Isaikina, O. Ya.,Lunin
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- Synthesis of hydrogen polyoxides H2O4 and H 2O3 and their characterization by raman spectroscopy
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Hydrogen tetroxide (H2O4) and hydrogen trioxide (H2O3) have been prepared in relatively large quantities as components of peroxy radical condensates. The polyoxides were characterized by the Raman spectra of the oxygen framework. Lines at 500, 756, and 878 cm -1 correspond to skeletal oscillations of H2O3 in the condensate (OOO bend, asymmetric OO stretch, symmetric OO stretch). Lines at 449, 589, 624, 827, and 865 cm-1 match the skeletal vibrations of H2O4 (OOO bend 1, OOO bend 2, center OO stretch, asymmetric OO stretch, symmetric OO stretch). The line of the O4 torsion vibration of hydrogen tetroxide was not observed experimentally. The assignment was confirmed by B3LYP/6-31+G(d,p) calculations of the vibrational spectra. According to the information available in the literature, this work is the only report of the preparation of H2O4 in significant concentrations and its Raman spectrum. For the first time convincing evidence is provided for the existence of hydrogen tetroxide (in low-temperature solids). Copyright
- Levanov, Alexander V.,Sakharov, Dmitri V.,Dashkova, Anna V.,Antipenko, Ewald E.,Lunin, Valeri V.
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- Dihydrogen trioxide (HOOOH) photoelimination from a platinum(IV) hydroperoxo-hydroxo complex
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Photolysis (380 nm) of trans-Pt(PEt3)2(Cl)(OH)(OOH)(4-trifluoromethylphenyl) (1) at -78 °C in acetone-d6 or toluene-d8 yields HOOOH (16-20%) and trans-Pt(PEt3)2(Cl)(4-trifluoromethylphenyl) (2). Also observed in acetone-d6 are H2O2, (CD3)2C(OH)(OOH), and (CD3)2C(OOH)2. Thermal decomposition or room-temperature photolysis of 1 gives O2, water, and 2. Computational modeling (DFT) suggests two intramolecular hydrogen-bonding-dependent triplet pathways for the photolysis and two possible pathways for the thermolysis, one involving proton transfer from the OOH to the OH ligand and the other homolysis of the Pt-OOH bond, abstraction of the OH ligand, and decomposition of the resulting H2O3. Trapping studies suggest the latter pathway.
- Wickramasinghe, Lasantha A.,Sharp, Paul R.
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supporting information
p. 13979 - 13982
(2015/01/08)
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- The ozonation of silanes and germanes: An experimental and theoretical investigation
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Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3-SiOOOH and R3GeOOOH, which were characterized by 1H, 13C, 17O, and 29Si NMR, and by infrared spectroscopy in a two-pronged approach based on measured and calculated data. Ozone reacts with the E-H (E = Si, Ge) bond via a concerted 1,3-dipolar insertion mechanism, where, depending on the substituents and the environment (e.g., acetone-d6 solution), the H atom transfer precedes more and more E-O bond formation. The hydrotrioxides decompose in various solvents into the corresponding silanols/germanols, disiloxanes/digermoxanes, singlet oxygen (O2(1Δ g)), and dihydrogen trioxide (HOOOH), where catalytic amounts of water play an important role as is indicated by quantum chemical calculations. The formation of HOOOH as a decomposition product of organometallic hydrotrioxides in acetone-d6 represents a new and convenient method for the preparation of this simple, biochemically important polyoxide. By solvent variation, singlet oxygen (O2(1Δ g)) can be generated in high yield.
- Cerkovnik, Janez,Tuttle, Tell,Kraka, Elfi,Lendero, Nika,Plesnicar, Bozo,Cremer, Dieter
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p. 4090 - 4100
(2007/10/03)
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- Mechanism of formation of hydrogen trioxide (HOOOH) in the ozonation of 1,2-diphenylhydrazine and 1,2-dimethylhydrazine: An experimental and theoretical investigation
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Low-temperature (-78 °C) ozonation of 1,2- diphenylhydrazine in various oxygen bases as solvents (acetone-d6, methyl acetate, tert-butyl methyl ether) produced hydrogen trioxide (HOOOH), 1,2-diphenyldiazene, 1,2-diphenyldiazene-N-oxide, and hydrogen peroxide. Ozonation of 1,2-dimethylhydrazine produced besides HOOOH, 1,2-dimethyldiazene, 1,2-dimethyldiazene-N-oxide and hydrogen peroxide, also formic acid and nitromethane. Kinetic and activation parameters for the decomposition of the HOOOH produced in this way, and identified by 1H, 2H, and 17O NMR spectroscopy, are in agreement with our previous proposal that water participates in this reaction as a bifunctional catalyst in a polar decomposition process to produce water and singlet oxygen (O2, 1Δg). The possibility that hydrogen peroxide is, besides water, also involved in the decomposition of hydrogen trioxide is also considered. The half-life of HOOOH at room temperature (20 °C) is 16 ± 1 min in all solvents investigated. Using a variety of DFT methods (restricted, broken-symmetry unrestricted, self-interaction corrected) in connection with the B3LYP functional, a stepwise mechanism involving the hydrotrioxyl (HOOO.) radical is proposed for the ozonation of hydrazines (RNHNHR, R = H, Ph, Me) that involves the abstraction of the N-hydrogen atom by ozone to form a radical pair, RNNHR..OOOH. The hydrotrioxyl radical can then either abstract the remaining N(H) hydrogen atom from the RNNHR. radical to form the corresponding diazene (RN=NR), or recombines with RNNHR. in a solvent cage to form the hydrotrioxide, RN(OOOH)NHR. The decomposition of these very labile hydrotrioxides involves the homolytic scission of the RO-OOH bond with subsequent in cage formation of the diazene-N-oxide and hydrogen peroxide. Although 1,2-diphenyldiazene is unreactive toward ozone under conditions investigated, 1,2-dimethyldiazene reacts with relative ease to yield 1,2-dimethyldiazene-N-oxide and singlet oxygen (O2, 1Δg). The subsequent reaction sequence between these two components to yield nitromethane as the final product is discussed. The formation of formic acid and nitromethane in the ozonolysis of 1,2-dimethylhydrazine is explained as being due to the abstraction of a methyl H atom of the CH3NNHCH3. radical by HOOO . in the solvent cage. The possible mechanism of the reaction of the initially formed formaldehyde methylhydrazone (and HOOOH) with ozone/oxygen mixtures to produce formic acid and nitromethane is also discussed.
- Plesnicar, Bozo,Tuttle, Tell,Cerkovnik, Janez,Koller, Joze,Cremer, Dieter
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p. 11553 - 11564
(2007/10/03)
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- Evidence for HOOO radicals in the formation of alkyl hydrotrioxides (ROOOH) and hydrogen trioxide (HOOOH) in the ozonation of C - H bonds in hydrocarbons
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Low-temperature ozonation of cumene (1a) in acetone, methyl acetate, and tert-butyl methyl ether at -70° C produced the corresponding hydrotrioxide, C6H5C(CH3)2OOOH (2a), along with hydrogen trioxide, HOOOH. Ozonation of triphenylmethane (1b), however, produced only triphenylmethyl hydrotrioxide, (C6H5)3COOOH (2b). These observations, together with the previously reported experimental evidence, seem to support the "radical" mechanism for the first step of the ozonation of the C - H bonds in hydrocarbons, i.e., the formation of the caged radical pair (R??OOOH), which allows both (a) collapse of the radical pair to ROOOH and (b) the abstraction of the hydrogen atom from alkyl radical R? by HOOO? to form HOOOH. The B3LYP/6-311++G(d,p) (ZPE) calculations revealed that HOOO radicals are considerably stabilized by forming intermolecularly hydrogen-bonded complexes with acetone (BE = 8.55 kcal/mol) and dimethyl ether (7.04 kcal/mol). This type of interaction appears to be crucial for the relatively fast reactions (and the formation of the polyoxides in relatively high yields) in these solvents, as compared to the ozonations run in nonbasic solvents. However, HOOO radicals appear to be not stable enough to abstract hydrogen atoms outside the solvent cage, as indicated by the absence of HOOOH among the products in the ozonolysis of triphenylmethane. The decomposition of alkyl hydrotrioxides 2a and 2b involves a homolytic cleavage of the RO-OOH bond with subsequent "in cage" reactions of the corresponding radicals, while the decomposition of HOOOH is most likely predominantly a "pericyclic" process involving one or more molecules of water acting as a bifunctional catalyst to produce water and singlet oxygen (Δ1O2).
- Cerkovnik, Janez,Erzen, Evgen,Koller, Joze,Plesnicar, Bozo
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p. 404 - 409
(2007/10/03)
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