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A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack

A-234, [EtO–P([double bond, length as m-dash]O)(F)–N[double bond, length as m-dash]C(Me)–N(Et)(2)], is the suspected A-type nerve agent used in the Skripal attack on the 4th of March 2018. Studies related to the structure and reactivity of this compound are limited. We, therefore, aimed at understan...

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Autores principales: Imrit, Yadhav A., Bhakhoa, Hanusha, Sergeieva, Tetiana, Danés, Sergi, Savoo, Nandini, Elzagheid, Mohamed I., Rhyman, Lydia, Andrada, Diego M., Ramasami, Ponnadurai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9055627/
https://www.ncbi.nlm.nih.gov/pubmed/35519147
http://dx.doi.org/10.1039/d0ra05086e
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author Imrit, Yadhav A.
Bhakhoa, Hanusha
Sergeieva, Tetiana
Danés, Sergi
Savoo, Nandini
Elzagheid, Mohamed I.
Rhyman, Lydia
Andrada, Diego M.
Ramasami, Ponnadurai
author_facet Imrit, Yadhav A.
Bhakhoa, Hanusha
Sergeieva, Tetiana
Danés, Sergi
Savoo, Nandini
Elzagheid, Mohamed I.
Rhyman, Lydia
Andrada, Diego M.
Ramasami, Ponnadurai
author_sort Imrit, Yadhav A.
collection PubMed
description A-234, [EtO–P([double bond, length as m-dash]O)(F)–N[double bond, length as m-dash]C(Me)–N(Et)(2)], is the suspected A-type nerve agent used in the Skripal attack on the 4th of March 2018. Studies related to the structure and reactivity of this compound are limited. We, therefore, aimed at understanding the underlying hydrolysis mechanism of A-234 within the DFT framework. The attack of the water molecule can occur at the phosphinate and acetoamidine reactive centres. Our theoretical findings indicate that the hydrolysis at the acetoamidine centre is thermodynamically favoured compared to the hydrolysis at the phosphinate centre. The hydrolysis at the acetoamidine moiety may proceed via two pathways, depending on the nitrogen atom participating in the hydrolysis. The main pathway consists of four distinct channels to reach the final product, with the concerted 1,3-proton shift favoured kinetically and thermodynamically in the gas phase and water as solvent. The results are in good agreement with the literature, although some differences in the reaction mechanism were observed.
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spelling pubmed-90556272022-05-04 A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack Imrit, Yadhav A. Bhakhoa, Hanusha Sergeieva, Tetiana Danés, Sergi Savoo, Nandini Elzagheid, Mohamed I. Rhyman, Lydia Andrada, Diego M. Ramasami, Ponnadurai RSC Adv Chemistry A-234, [EtO–P([double bond, length as m-dash]O)(F)–N[double bond, length as m-dash]C(Me)–N(Et)(2)], is the suspected A-type nerve agent used in the Skripal attack on the 4th of March 2018. Studies related to the structure and reactivity of this compound are limited. We, therefore, aimed at understanding the underlying hydrolysis mechanism of A-234 within the DFT framework. The attack of the water molecule can occur at the phosphinate and acetoamidine reactive centres. Our theoretical findings indicate that the hydrolysis at the acetoamidine centre is thermodynamically favoured compared to the hydrolysis at the phosphinate centre. The hydrolysis at the acetoamidine moiety may proceed via two pathways, depending on the nitrogen atom participating in the hydrolysis. The main pathway consists of four distinct channels to reach the final product, with the concerted 1,3-proton shift favoured kinetically and thermodynamically in the gas phase and water as solvent. The results are in good agreement with the literature, although some differences in the reaction mechanism were observed. The Royal Society of Chemistry 2020-07-27 /pmc/articles/PMC9055627/ /pubmed/35519147 http://dx.doi.org/10.1039/d0ra05086e Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Imrit, Yadhav A.
Bhakhoa, Hanusha
Sergeieva, Tetiana
Danés, Sergi
Savoo, Nandini
Elzagheid, Mohamed I.
Rhyman, Lydia
Andrada, Diego M.
Ramasami, Ponnadurai
A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title_full A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title_fullStr A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title_full_unstemmed A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title_short A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack
title_sort theoretical study of the hydrolysis mechanism of a-234; the suspected novichok agent in the skripal attack
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9055627/
https://www.ncbi.nlm.nih.gov/pubmed/35519147
http://dx.doi.org/10.1039/d0ra05086e
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