Effect of sulfuric acid on reactions of peroxymonosulfate ion with sulfides and thiol esters

A detailed analysis of the global and local reactivity patterns of neutral and charged peroxides, including hydrogen peroxide (HOOH), peroxynitric acid (HOONO 2 ), the peroxymonocarbonic ion (HOOCO 2 -), and the peroxymonosulfate ion (HOOSO 3 -) in the presence of a polar solvent (water) is presented. The polar solvent effects are included using an isodensity surface polarized continuum model (IPCM). The (1,2) hydrogenshift reaction for these peroxides is studied. The transition states involved in the (1,2) hydrogen shift have been located and characterized at the B3LYP/6-311G** level of theory. The global analysis shows that, although the replacement of one hydrogen atom in HOOH by a neutral NO 2 group enhances both the global softness and global electrophilicity, the substitution of one hydrogen atom by charged CO 2and SO 3groups results in a significant electrophilic deactivation of HOOCO 2and a moderate electrophilic activation of HOOSO 3 -. This result is observed in both the ground state and in some activated forms involved in the (1,2) hydrogen rearrangement. The local analysis, however, shows that the transition-state structures for the same rearrangement of HOOH and the HOOCO 2ion display an electrophilicity-enhanced pattern at the oxygen atom that is being deprotonated, thereby suggesting that this activated form is more likely to be involved in the oxygen-transfer reactions. The site-activation analysis performed on the basis of the variations in local softness from the ground to the transition states is also consistent with this local reactivity picture.

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Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO₂, CO₂^-, SO₃^-) Peroxides with Solvent Effects

Aparicio

Contreras

Galván

et al. 2003

J. Phys. Chem. A

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Reactions of aryl sulfides and phosphorus(V) esters of thiols with acidic hydrogen peroxide

Bunton¹,

Foroudian²,

Gillitt³

et al. 1999

Can. J. Chem.

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Oxidations of sulfides and phosphorus(V) esters of thiols by H2O2 are catalyzed by H2SO4 and HClO4. Sulfides are 4-ZC6H4SMe, 1a-1e, respectively, Z = MeO, Me, H, Cl, NO2; PhSCH2CH2Cl, 2, Ph2S, 3, and the esters are Ph(R)PO·SEt, 4a, 4b, R = Ph, EtO. Electron donation by Z moderately accelerates reaction, but the sulfides are much more reactive than the esters. Reactions are first order in H2O2 and substrate, and second-order rate constants, k2, in H2SO4 are related to excess acidity, X. Plots of log k2 against X have slopes in the range 0.61-0.85. Rate constants are similar for given concentrations of H2SO4 and HClO4, except that with greater than 50 wt.% H2SO4 peroxymonosulfuric acid is formed and the observed rate constants then increase. Methanesulfonic acid is a less effective catalyst than the mineral acids. Oxidations of the sulfides are also catalyzed by strongly acidic ion-exchange resins.Key words: sulfide oxidation, hydrogen peroxide, acid catalysis, excess acidity.

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Effect of sulfuric acid on reactions of peroxymonosulfate ion with sulfides and thiol esters

Cited by 2 publications

References 31 publications

Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO₂, CO₂^-, SO₃^-) Peroxides with Solvent Effects

Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO₂, CO₂^-, SO₃^-) Peroxides with Solvent Effects

Reactions of aryl sulfides and phosphorus(V) esters of thiols with acidic hydrogen peroxide

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Effect of sulfuric acid on reactions of peroxymonosulfate ion with sulfides and thiol esters

Cited by 2 publications

References 31 publications

Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO2, CO2-, SO3-) Peroxides with Solvent Effects

Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO2, CO2-, SO3-) Peroxides with Solvent Effects

Reactions of aryl sulfides and phosphorus(V) esters of thiols with acidic hydrogen peroxide

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Product

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Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO₂, CO₂^-, SO₃^-) Peroxides with Solvent Effects

Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO₂, CO₂^-, SO₃^-) Peroxides with Solvent Effects