MICROWAVE SPECTRA AND STRUCTURES OF AMINODIFLUORO PHOSPHINE AND CHLORODIFLUOROPHOSPHINE
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Date
1970
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Publisher
Ohio State University
Abstract
The microwave spectra of $PF_{2}^{14} NH_{1}$, $PF_{2}^{12} NH_{2}$, $PF_{2}NHD$^{\prime} and $PF_{2}NDH$^{\prime} have been assigned and from these the structure of the molecule has been determined. The phosphorous, nitrogen and hydrogen atoms appear to lie in the symmetry plane of the molecule and the structural parameters obtained are: $r_{PF}=1.586$ {\AA}, $r_{PN}=1.647$ {\AA} $r_{NH(cis)}=1.000$ {\AA}, $r_{NH(trass)}=0.983$ {\AA}, $<{FPF}=94.7^\circ$. $<{FPN}=100.7^\circ$, $<{HNH}=117.6^\circ$, $< PNH_{cis}^\circ=122.9^\circ$ and $< PNH_{tanss}=119.5^\circ$. The dipole moment components are found to be $\mu_{s}=2.57 D$ and $\mu_{e}=0.18 D$ giving a total dipole $\mu$=2.58D. Analysis of the hyperfine structure on transitions for $PF_{2}^{14} NH_{2}$ yielded the quadrupole coupling constants $\chi_{aa} = 1.65$ MHz, $\chi_{bb} = -3.45$ MHz and $\chi_{cc} = 1.80$ MHz. Torsional satellites have been seen and the results of an investigation of them will be reported. The structure of chlorodifluorophosphine was determined following the assignment of the microwave spectra of $PF_{2}^{23}Cl$ and $PF_{2}^{27}Cl$. The structural parameters are: $r_{PF}=1.571$ \AA, $r_{PCI}=2.030$ \AA. $<{FPF}=97.3^\circ$ and $<{FPCl}=99.2^\circ$. The dipole moment components are determined to be $\mu_{a}=0.11 D$ and $\mu_{e}$=0.87D giving a total dipole $\mu$=0.88D. The quadrupole coupling constants in $PF_{2}^{25}Cl$ are $\chi_{aa}= -39.3$ MHz, $\chi_{bb}=20.7$ MHz and $\chi_{cc}=18.6$ MHz, while for $PF_{2}^{37}Cl$, $\chi_{aa}= 0-1.31$ MHz, $\chi_{bb}= 16.6$ MHz and $\chi_{cc}= 14.5$ MHz.
Description
Author Institution: Department of Chemistry, Michigan State University