Abstract
Abstract Chlorine nuclear quadrupole resonance spectra determined at 77°K. and F19 n.m.r. data obtained as a function of temperature for the molecular forms of PCl4,F, PCl3F2, and PCl2F3 were correlated with previous infrared and Raman spectra. The data support the trigonal bipyramid as the structural model for the halides with fluorine atoms showing a preference for axial positions. The symmetry of PCl4F is C3v and that of PCl3F2 is D3h. For PCl2F3 the data are best interpreted in terms of the C2v point group. Further, the data give no evidence for any significant variation in molecular structure between the gas, liquid, and solid states. Symmetry considerations and the F19 n.m.r. data support the presence of axial P‒F π-bonding. The chlorine quadrupole data indicate a lesser importance of π-bonding in the P‒Cl bonds.
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