Heterogeneous Organophosphate Ethanolysis: Degradation of Phosphonothioate Neurotoxin by a Supported Molybdenum Peroxo Polymer
| العنوان: | Heterogeneous Organophosphate Ethanolysis: Degradation of Phosphonothioate Neurotoxin by a Supported Molybdenum Peroxo Polymer |
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| المؤلفون: | Andrew Bennett, Qianli Miao, Louis Y. Kuo |
| المصدر: | Inorganic Chemistry. 56:10013-10020 |
| بيانات النشر: | American Chemical Society (ACS), 2017. |
| سنة النشر: | 2017 |
| مصطلحات موضوعية: | Polymers, Neurotoxins, Molybdate, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, Medicinal chemistry, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Nucleophile, Coordination Complexes, Organic chemistry, Reactivity (chemistry), Physical and Theoretical Chemistry, Bond cleavage, Molybdenum, Ethanol, 010405 organic chemistry, Chemistry, Thioanisole, Hydrogen Peroxide, Phosphonate, 0104 chemical sciences, Models, Chemical, Organothiophosphonates, Oxidation-Reduction |
| الوصف: | 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) (Ea = 57 ± 6 kJ/mol and ΔS⧧ = -124 ± 21 J/mol·K) and by the model compound oxodiperoxo(pyridine-2-carboxylato)molybdate(VI) bis(pyridine-2-carboxylic acid) monohydrate (3; Ea = 55 ± 5 kJ/mol and ΔS⧧ = -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. |
| تدمد: | 1520-510X 0020-1669 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::23c8a85e0587364eaba5cbd488c9ed91 https://doi.org/10.1021/acs.inorgchem.7b01545 |
| رقم الأكسشن: | edsair.doi.dedup.....23c8a85e0587364eaba5cbd488c9ed91 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 1520510X 00201669 |
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