{"title":"P−F Bond Activation of Organophosphates by [(iPrPNHP)Mn(CO)2]+","authors":"Mario Prejanò, Marirosa Toscano, Tiziana Marino","doi":"10.1002/ejic.202400308","DOIUrl":null,"url":null,"abstract":"<p>Organophosphate compounds (OPC) are chemical species with a broad range of applications from agricultural to medicinal chemistry, which however rose sadly to the fore for their use as chemical weapons worldwide. Several efforts are therefore carried out to contrast their toxic effects or to repurpose OPC for chemical synthesis. In this regard, metal-containing systems, like metal-organic frameworks or complexes, represent a valid solution for the treatments of OPC in a number of fields. Our work has been inspired by the recent findings concerning the reactivity of (<sup>iPr</sup>PN<sup>H</sup>P)Mn(CO)<sub>2</sub>(OH) (<b>1</b>) complex with P−F bond containing organophosphate compounds. We, in particular, have investigated three different OPC, which are diisopropylfluorophosphate (<b>a</b>), isopropylfluorophosphoric acid (<b>b</b>) and fluorophosphoric acid (<b>c</b>), extending the complex <b>1</b> reactivity to the nerve gas sarin (<b>sa</b>). The reaction concerns the leaving of fluoride from OPC, to produce relative defluorinated phosphates and the (<sup>iPr</sup>PN<sup>H</sup>P)Mn(CO)<sub>2</sub>(F) complex. Analysis of the calculations revealed that the reaction is favored from both thermodynamic and kinetical points of view for <b>a</b> substrate. Our results are in agreement with the available experimental data and represent a further confirmation of versatility of such metal-complex to interact with P−F containing toxic agents.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 34","pages":""},"PeriodicalIF":2.2000,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400308","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ejic.202400308","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Organophosphate compounds (OPC) are chemical species with a broad range of applications from agricultural to medicinal chemistry, which however rose sadly to the fore for their use as chemical weapons worldwide. Several efforts are therefore carried out to contrast their toxic effects or to repurpose OPC for chemical synthesis. In this regard, metal-containing systems, like metal-organic frameworks or complexes, represent a valid solution for the treatments of OPC in a number of fields. Our work has been inspired by the recent findings concerning the reactivity of (iPrPNHP)Mn(CO)2(OH) (1) complex with P−F bond containing organophosphate compounds. We, in particular, have investigated three different OPC, which are diisopropylfluorophosphate (a), isopropylfluorophosphoric acid (b) and fluorophosphoric acid (c), extending the complex 1 reactivity to the nerve gas sarin (sa). The reaction concerns the leaving of fluoride from OPC, to produce relative defluorinated phosphates and the (iPrPNHP)Mn(CO)2(F) complex. Analysis of the calculations revealed that the reaction is favored from both thermodynamic and kinetical points of view for a substrate. Our results are in agreement with the available experimental data and represent a further confirmation of versatility of such metal-complex to interact with P−F containing toxic agents.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
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