Novel onium salts. Synthesis and characterization of the peroxonium cation H2OOH

Wilson, William W.; Curtis, E. C.

doi:10.1021/ic50199a049

Cited by 39 publications

(16 citation statements)

References 15 publications

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“…is so little basic that even at pH = -0.3 to 2 potentiometric titration, carried out as described [2], fails to demonstrate the formation of the species HSO; in detectable amounts. The species H30: was isolated in the form of salts such as [H30:][SbF;] in nonaqueous solvents [3]. The pK, of H30$ is hitherto unknown.…”

Section: Methodsmentioning

confidence: 99%

Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

Drexler

Elias

Fecher

et al. 1992

Ber Bunsenges Phys Chem

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Similar results were observed when Mn(I1) is added to the Fe(I1) system, the effect being most significant in the presence of some initially added Fe(II1). A series of typical results for the sulfite induced autoxidation of Fe(I1) as a function of Mn(I1) concentration are reported in Fig. 6. In this case the Mn(I1) effect seems to exhibit a square dependence on its concentration. Although the details of this synergistic effect are not well understood at present, the observed Mn(I1) dependence may suggest the participation of dimeric species. Again the reaction of Fe(II1) with Mn(I1) t o produce Fe(I1) and Mn(II1) can initiate the overall sulfite induced autoxidation of Fe(I1). ConclusionsThe work described in this report has resolved important aspects of the autoxidation of metal ions that is needed in order to complete the catalytic cycle for metal catalyzed autoxidation reactions of S(IV) oxides. The remarkable finding that sulfite can induce such oxidation processes and the resulting redox cycling of the metal ions may be of significance in accounting for the importance of such reactions in atmospheric oxidation processes. The relative concentration ratio of oxygen (or another oxidant such as H202 or 0,) and sulfite determines the oxidation state and the catalytic activity of the investigated metal ions. This concentration ratio will vary under atmospheric conditions depending on the oxygen and sulfite levels present, and as such have a dynamic effect on the overall autoxidation chemistry.The authors gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft, Bundesministerium fur Forschung und Technologie, and Commission of the European Communities. a) On leave from the Stopped-flow spectrophotometry was used to study the oxidation of S(IV) by H202 at 285 K and 298 K, respectively, in the pH range -0.3 to 13 in buffered aqueous solution under pseudo-first-order conditions (I = 0.5, 1.0 and 2.0 M NaC104, respectively). The reaction of HSOT with H202 is subject to generalacid catalysis whereas that of the s@,ion is not. The dependence of the experimental first-order rate constant on the concentration of the excess partner [H202] was studied in detail. -In the pH range -0.3 to 6 the rate is given by Eq. (1) (KRl and Ksl: acid dissociation constants of H302+ and SO2, respectively; [HI = proton activity).

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Section: Methodsmentioning

confidence: 99%

Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

Drexler

Elias

Fecher

et al. 1992

Ber Bunsenges Phys Chem

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“…96 (lYY2) No. 3 thermore, due to the low temperatures of the host matrix (typically 4-30 K) high energetic intermediates are quasi stable and their characterization can be achieved by a variety of spectroscopic methods.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric Reactions in Cryogenic Matrices: Photooxidation of Carbonyl Sulfide (SCO) by Ozone

Jaeger

Weller

Schrems

1992

Ber Bunsenges Phys Chem

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Photooxidation of carbonyl sulfide (SCO) in the presence of ozone has been studied in solid matrices under stratospheric irradiation conditions. The matrix experiments allowed the isolation and identification of SCO ' 0 , 1 : 1 aggregates. Selective photolysis of O3 yielded O('D) atoms and subsequent reaction with SCO resulted in the primary formation of C 0 2 + S. The sulfur atoms generated this way are oxidized to SO? by 02, which has been formed during photofragmentation of 03. In further steps SO2 reacted with diffusing 0 atoms to SO3 and SO4. Experiments with isotopically labeled precursors confirmed the conclusions that the photolysis of "0,. SCO hetero-complexes leads to SlSO2, S1803, and '60C'80 formation.

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“…Since the hindrance of rotation of the phenyl groups in cation 45a is much less, no splitting is observed. They exothermically decompose at room temperature to hydronium ion salt and molecular oxygen127 [Eq. The hydrogen peroxonium ion H 3 O 2 þ 46 has been invoked as an intermediate in the electrophilic hydroxylation of aromatics, oxygenation of alkanes, and so on 126.…”

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confidence: 99%

Heterocations in Superacid Systems

Oláh¹,

Prakash²,

Molnár³

et al. 2008

Superacid Chemistry

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Novel onium salts. Synthesis and characterization of the peroxonium cation H2OOH

Cited by 39 publications

References 15 publications

Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

Kinetics and Mechanism of Sulfur(IV) Oxidation by Hydrogen Peroxide in Aqueous Phase: The Non‐Linear Parts of the pH‐Profile

Atmospheric Reactions in Cryogenic Matrices: Photooxidation of Carbonyl Sulfide (SCO) by Ozone

Heterocations in Superacid Systems

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