NORMAL COORDINATE TREATMENTS OF PHOSPHORYL HALIDES
Publisher:
Ohio State UniversityAbstract:
The infrared and Raman spectra for phosphoryl chloride, thiophosphoryl chloride, phosphoryl fluoride, and thiophosphoryl fluoride were collected and examined for the probable values for the wave numbers $(\Delta\sigma)$, relative intensities I, and depolarization factors $\rho$. The $\Delta\sigma$ (I) $\rho$ values adopted are as follows: for $POCl_{3}$: 192.85 (8) 0.83, 267.39 (6) 0.64, 337.44 (7) 0.81, 486.24 (10) 0.05, 581.2 (3) 6/7, and 1289.9K (5) 0.04; for $PSCl_{3}$: 172 (5) 6/7, 247 (7) 6/7, 247 (calculated) 430 (10) 0.1, 538 (1) 6/7, and 753 K (1) P; for $POF_{3}$: 337 (W) 6/7, 467 (m) 6/7, 483 (-) P (from infrared), 875 (S) 0.05, 982 (VW) 6/7, and 1395 K (m) 0.1; for $PSF_{3}$: 940 (-) D, 874 (-) P, 695 (-) P, 440 (-) P, 402 (-) B, and 276 D. The infrared spectral data used were that of O. Cilento et. al for $PSCl_{3}$ and that of Gutowsky and Liehr for $POF_{3}$. No data were found for $POCl_{3}$ and $PSF_{3}$. Normal coordinate treatments ($C_{3\nu}$ model) were made for $POCl_{3}$, $PSCl_{3}$, $POF_{3}$, and $PSF_{3}$. These gave calculated fundamentals which agree well with the values listed above and lend support for the 247 K for $PSCl_{3}$ and 483 K for $POF_{3}$ as the missing Raman lines. The F-matrix elements were determined in such a manner that potential constants for the $PCl_{3}$ group had nearly the same values in $POCl_{3}$ and $PSCl_{3}$, those for the $PF_{3}$ group had nearly the same values in $POF_{3}$ and $PSF_{3}$,the one for the PO group had nearly the same value in $POCl_{3}$ and $POF_{3}$, and the one for the PS group had nearly the same value in $PSF_{3}$ and $PSCl_{3}$. In addition to these halides, $PFCl_{2}$ and $POFCl_{2}$ were considered. In this latter case the potential constants for $PFCl_{2}$ were correlated with those of $PF_{3}$ and $PCl_{3}$ and were used in the determination of the F-matrix elements for $POFCl_{2}$ in the same manner as given above.
Description:
Author Institution: Chemistry Department, De Paul University
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articleOther Identifiers:
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