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        Synthesis, conductivity, and vibrational spectroscopy of tetraphenylphosphonium bis(trifluoromethanesulfonyl)imide

        Haddad, Boumediene,Paolone, Annalisa,Villemin, Didier,Taqiyeddine, Moumene,Belarbi, El-habib,Bresson, Serge,Rahmouni, Mustapha,Dhumal, Nilesh R.,Kim, Hyung J.,Kiefer, Johannes Elsevier 2017 Journal of molecular structure Vol.1146 No.-

        <P><B>Abstract</B></P> <P>The reaction of lithium bis(trifluoromethanesulfonyl)imide with tetraphenylphosphonium bromide in water leads to the formation of tetraphenylphosphonium bis(trifluoromethanesulfonyl)imide ([PPh<SUB>4</SUB> <SUP>+</SUP>][(CF<SUB>3</SUB>SO<SUB>2</SUB>)<SUB>2</SUB>N<SUP>−</SUP>]). The obtained compound was identified by means of <SUP>1</SUP>H, <SUP>13</SUP>C, <SUP>19</SUP>F and <SUP>31</SUP>P NMR spectroscopy. Although it has a structure similar to ionic liquids, it exhibits a melting point above 100 °C. Besides describing the synthesis, a detailed characterization of its conductivity and vibrational spectroscopic properties is presented. For the latter, FT-Raman and FTIR/ATR spectroscopies are used in the wavenumber range from 150 to 3500 cm<SUP>−1</SUP> and from 600 to 3500 cm<SUP>−1</SUP>, respectively. Density functional theory calculations reveal a minor influence of the interionic interactions on the vibrational structure. Consequently, the computational vibrational spectra of the isolated ions show a good agreement with the experimental data. A detailed vibrational assignment is presented. Furthermore, the conductivity data indicate a solid-solid phase transition about 130 K below the melting point.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Conductivity data indicate a solid-solid phase transition. </LI> <LI> Interionic interactions play a minor role in the vibrational structure of PPh<SUB>4</SUB> NTf<SUB>2</SUB>. </LI> <LI> Computational and experimental spectra agree well. </LI> </UL> </P>

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