P−F Bond Activation of Organophosphates by [( ^iPr PN ^H P)Mn(CO) ₂ ] ⁺

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 ( iPr PN H P)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 ( iPr PN H P)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.