Role of the P-F bond in fluoride-promoted aqueous VX hydrolysis: an experimental and theoretical study.
Following our ongoing studies on the reactivity of the fluoride ion toward organophosphorus compounds, we established that the extremely toxic and environmentally persistent chemical warfare agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is exclusively and rapidly degraded to the nontoxic product EMPA (ethyl methylphosphonic acid) even in dilute aqueous solutions of fluoride. The unique role of the P-F bond formation in the reaction mechanism was explored using both experimental and computational mechanistic studies. In most cases, the "G-analogue" (O-ethyl methylphosphonofluoridate, Et-G) was observed as an intermediate. Noteworthy and of practical importance is the fact that the toxic side product desethyl-VX, which is formed in substantial quantities during the slow degradation of VX in unbuffered water, is completely avoided in the presence of fluoride. A computational study on a VX-model, O,S-diethyl methylphosphonothioate (1), clarifies the distinctive tendency of aqueous fluoride ions to react with such organophosphorus compounds. The facility of the degradation process even in dilute fluoride solutions is due to the increased reactivity of fluoride, which is caused by the significant low activation barrier for the P-F bond formation. In addition, the unique nucleophilicity of fluoride versus hydroxide toward VX, in contrast to their relative basicity, is discussed. Although the reaction outcomes were similar, much slower reaction rates were observed experimentally for the VX-model (1) in comparison to VX.
Department of Organic Chemistry, Israel Institute for Biological Research, Ness-Ziona, 74100, Israel.
Daniele
D
Marciano
Ishay
I
Columbus
Shlomi
S
Elias
Michael
M
Goldvaser
Ofir
O
Shoshanim
Nissan
N
Ashkenazi
Yossi
Y
Zafrani
D005459:Fluorides / Q000737:chemistry; D006868:Hydrolysis; D007700:Kinetics; D008962:Models, Theoretical; D009946:Organothiophosphorus Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D005459:Fluorides; D009946:Organothiophosphorus Compounds; D014867:Water; C009680:VX-agent