The possibility of designing a solvent/reagent for Wittig reactions from basic phosphonium salts is explored theoretically. In the suggested R4P+PhO– and Ph3PR+PhO– ionic liquids (ILs), the phenolate anion is prone to remove the α-proton from the alkyl chains, forming a phosphorous ylide. Significant hydrogen bonding between the oxygen atoms of the anions and α-hydrogen atoms of the cations were found by molecular dynamics simulations of these substances; therefore, proton transfer between the two ions is inherently supported by the structure of the liquid as well. The subsequent steps of the Wittig reaction from the phosphorous ylide were also found to be energetically possible. The mesoscopic structure of these materials exhibits a significant segregation into polar and nonpolar domains, which may also allow an easy dissolution of the substrates. The formation of a pentacoordinated phosphorous derivative through P–O bond formation was found to be also possible in the gas phase for both kind of compounds. Accordingly, having such basic anions in phosphonium-based ILs may produce sucha neutral and therefore volatile species, which may hold further significantapplications for these solvents in ion-exchange and separation techniquesand in synthesis.
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