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Novel application of simple molybdates: Catalytic hydrolysis of an organophosphate neurotoxin under mild aqueous conditions.
- Source :
-
Inorganica Chimica Acta . Sep2017, Vol. 466, p1-7. 7p. - Publication Year :
- 2017
-
Abstract
- A novel protocol for hydrolyzing phosphonothioate neurotoxins has been developed that uses a readily available, inexpensive and non-toxic molybdate (MoO 4 2− ). The target organophosphate is O,S -diethylphenyl phosphonothioate ( 1 ), a model compound that has served as an analog of the chemical warfare agent VX. Molybdate-mediated hydrolysis of 1 proceeds at room temperature (pH ∼ 7.5) and yields a relatively safe phosphonate product through P-S specific scission. This is the first report of utilizing the molybdate, MoO 4 2− , to degrade an organophosphate neurotoxin with turnover. A ΔS ‡ of −81.5 J/mol·K (−19.5 cal/mol·K) indicates a bimolecular process, and 18 O-labeling studies show no oxygen exchange of 1 throughout the hydrolysis by MoO 4 2− ( aq ). We hypothesize primarily the monomeric molybdate is the active species at pH 7.5 where a S N 2(P) mechanism takes place. Density functional theory methods suggest the molybdate oxoanion serves as the nucleophile to attack phosphonothioate 1 to form a molybdate-phosphonate anhydride that subsequently hydrolyzes to the starting molybdate and phenylethyl phosphonate. [ABSTRACT FROM AUTHOR]
- Subjects :
- *NEUROTOXIC agents
*MOLYBDATES
*CHEMICAL warfare
*STYRENE
*MOLYBDENUM compounds
Subjects
Details
- Language :
- English
- ISSN :
- 00201693
- Volume :
- 466
- Database :
- Academic Search Index
- Journal :
- Inorganica Chimica Acta
- Publication Type :
- Academic Journal
- Accession number :
- 124820140
- Full Text :
- https://doi.org/10.1016/j.ica.2017.05.007