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Computational studies on the solvolysis of the chemical warfare agent VX
Author(s) -
Daniel Kelly A.,
Kopff Laura A.,
Patterson Eric V.
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1333
Subject(s) - chemistry , natural bond orbital , nerve agent , solvolysis , alkoxide , hydroxide , chemical warfare agents , nucleophile , computational chemistry , alkaline hydrolysis , density functional theory , hydrolysis , combinatorial chemistry , organic chemistry , biochemical engineering , catalysis , acetylcholinesterase , enzyme , engineering
The reaction of the chemical warfare agent VX with hydroxide and hydroperoxide has been studied using a combination of correlated molecular orbital and density functional theory. It is found that the alkaline hydrolysis leads to a mixture of neurotoxic and non‐toxic products while hydroperoxidolysis leads to exclusive formation of non‐toxic products. Natural bond orbital (NBO) analysis is used to rationalize the observation that hydroxide will attack opposite the alkoxide ligand, while hydroperoxide will attack opposite the thiolate. The current results are in good agreement with previous experimental and computational work and serve to clarify the mechanism for destruction of this highly potent nerve agent. Copyright © 2008 John Wiley & Sons, Ltd.