期刊
INORGANIC CHEMISTRY
卷 56, 期 16, 页码 10013-10020出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.7b01545
关键词
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资金
- NSF-RUI [CHE-1413090]
- NSF-TUES [DUE-1140940]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1413090] Funding Source: National Science Foundation
A polystyrene-supported molybdenum peroxo material [Mo-Y(s)] was applied toward the oxidative degradation of the organophosphate neurotoxin O,S-diethylphenyl phosphonothioate (1) through ethanolysis. In addition to the operational advantages of the heterogeneous reactivity, oxidative ethanolysis with a 10-fold excess of hydrogen peroxide yields only P-S bond scission to produce diethylphenyl phosphonate and ethyl sulfate. This is the first report of a molybdenum solid support that promotes the degradation of sulfur-containing organophosphate with the turnover benefits of heterogeneous catalysis. The activation parameters of 1 ethanolysis by Mo-Y(s) (E-a = 57 +/- 6 kJ/mol and Delta S-double dagger = -124 +/- 21 J/molK) and by the model compound oxodiperoxo(pyridine-2-carboxylato)molybdate(VI) bis(pyridine-2-carboxylic acid) monohydrate (3; E-a = 55 +/- 5 kJ/mol and Delta S-double dagger = -154 +/- 15 J/mol.K) are almost identical for the oxidation of thioanisole by 3. This suggests that the rate-determining step for 1 ethanolysis is sulfur oxidation to form an intermediate phosphonothioate S-oxide, which subsequently undergoes nucleophilic attack by the ethanol solvent to form diethylphenyl phosphonate and ethyl sulfate. Evidence for the formation of this S-oxide intermediate and the postulated ethanolysis mechanism is provided.
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