INFRARED MATRIX ISOLATION STUDIES OF THE TETRAFLUOROPHOSPHORANYL $PF_{4}{^{-}}$ ANION
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Date
1980
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Ohio State University
Abstract
Although $PF_{3}, PF_{5}$ and $PF_{+6}{^{-}}$ are stable, well characterized species, as is the four coordinate $PF^{+6}$ cation, the $PF_{4}{^{-}}$ anion has only recently been detected, and is relatively poorly characterized. It has bee observed in both mass spectrometry and ion cyclotron resonance, leading to a value for $\Delta H_{f}{^{0}} =-335$ Kcal/mole and a fluoride ion affinity of $PF_{3}$ of about 50 Kcal/mole. The $PF_{4}{^{-}}$ has now been synthesized by the salt/molecule matrix isolation technique. Reaction of CsF and $PF_{3}$ in an argon matrix leads to the appearance of four bands, at 620, 711, 781 and $790 cm^{-1}$. These bands have been assigned to the four P-F stretching vibrations of the $PF_{4}{^{-}}$ anion in a $C_{2y}$ structure analogous to SF. A study of the mixed chlorofluoro system gave similar results, but with a substantial decrease in yield as the number of chlorine atoms increased and fluorine atoms decreased.
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