SERGIO P O R T 0 COMMEMORATIVE ISSUE

Vibrational Spectra and Structure

of Organophosphorous Compounds
2O"fInfrared and Raman Spectra, Vibrational Assignment and
Normal Coordinate Calculations of Methyldifluorophosphine

J. R. Durig, A. E. Stanley$ and M. R. Jalilian

Department of Chemistry, University of South Carolina, Columbia, South Carolina 29208, USA

The Raman spectra of gaseous, liquid and solid CHJPFzand the infrared spectra of the gas and solid have been
recorded (3200-20 cm-'). The assignment of the 15 fundamentals is given and discussed and is based on the gas
phase infrared hand contours, depolarization values and group frequencies. A normal coordinate calculationwas
carried out by utilizing a modified valence force field to calculate the frequencies and the potential energy
distributions. Extensive mixing was found between the PF, stretching and CH3 rocking modes. The methyl
torsion was observed at 192 cm-' in the far-infrared spectrum of the gas and from this frequency a three-fold
barrier to internal rotation of 1.74 kcal mol-' was calculated. This value is compared to similar quantities in
several other group VA compounds and the observed trends are consistent with those for the corresponding
group IVA compounds.

INTRODUCTION Mid-IR spectra were recorded from 3200 to 200 cm-I

The complete vibrational spectrum of methyldifluoro-
phosphine has not been reported previously, although
Codding et al.' have recorded the far-IR spectrum of the
gas in the region from 450 to 250cm-'. For
methyldifluorophosphine, the two spectroscopic
investigation^'^^ which have been published deal with
structural aspects of this molecule. The microwave study
of this molecule by Codding et al.' reports a barrier to
internal rotation of 2.300 kcalmol-*, which is high
considering the periodic trends that have been
established in similar compounds. A complete vibra-
tional investigation of methyldifluorophosphine in
different phases, including a normal coordinate analysis
should provide significant information about the
fundamental vibrations, the barrier to internal rotation,
and allow a comparison to corresponding data on alkyl-
halophosphine and related compounds.
EXPERIMENTAL
The sample of CH3PF2 used in the present work was
prepared by the fluorination of CH3PC12 (Strem Chem-
icals) using antimony t r i f l ~ o r i d e . Preparation
~ and
sample handling was under vacuum at all times.
Purification was accomplished using a low temperature
vacuum fractionation column. The purity of the sample
was monitored by the comparison of the mid-IR
spectrum of the gas phase to the previously published
~pectrum.~
i.For paper 19 in this series, see J. R Durig and B. J Streusand, Appi.
Spectrosc. 34,65 11980).
f Taken in part from the thesis of A. E. Stanley which will be submitted
to the Department of Chemistry In partial fulfillment of the PhD
degree.
CCC-O377-0486/8 1/0010-0044 $04.00
44 JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981
using a Perkin-Elmer model 621 spectrophotometer
with an extended base which was purged with dry
nitrogen and calibrated with frequencies of atmospheric
water vapor4 and standard gases.5 The mid-IR spectra
are shown in Fig. 1. Spectra of the gas phase were
obtained using a 10 cm cell with CsI windows and 8 or
80 torr of sample pressure. The corresponding spectra of
the solid phase were obtained by condensing and
annealing the sample in a typical cold cell6 with outer
windows and sample substrate fashioned from CsI and
cooled by boiling nitrogen.
Far-IR spectra were recorded from 500 to 80 cm-'
using a Digilab FTS-15B Fourier transform IR inter-
ferometer. A 6.25 p m beamsplitter and a high pressure
Hg arc lamp source were used. Atmospheric water vapor
was removed from the spectrometer housing by purging
with dry nitrogen. Typical spectra are shown in Fig. 2.
Spectra of the gas phase were obtained using either a
12 cm cell with polyethylene windows or a standard 1 m
cell with polyethylene windows. Typical sample pres-
sures were 80 to 300 torr. Interferograms for both the
sample and empty reference cell were recorded 3000,
2.500, or 1000 times, averaged, and transformed using a
boxcar apodization. The spectra for the solid phase
were obtained using a cold cell6 with a silicon plate as
sample substrate and equipped with polyethylene
windows. The sample was condensed and annealed on
the silicon plate which was cooled by boiling nitrogen.
Resolution for the as hase was 0.5 or 0.25 cm-' and
for the solid, 2 cm- F. P
The Raman spectra were recorded on a Cary model
82 spectrophotometer equipped with the 514.5 nm line
from either the Spectra-Physics model 171 argon ion
laser or a Coherent Radiation model CR-8 argon ion
laser. Typical Raman spectra are shown in Fig. 3. For
studies in the liquid and solid phases, the laser power at
the sample was typically 0.5 W, whereas for the gas
@ Heyden & Son Ltd, 1981
 VIBRATIONAL SPECTRA AND STRUCTURE OF ORGANOPHOSPHOROUS COMPOUNDS
I 1 I I
3500 3000 2500
Wavenumber (cm-')
Figure 1. Mid-IR spectra of methyldifluorophosphine: (a) gaseous, approximately 8 and 80 torr; (b)solid.
phase studies, maximum power of 1.5 W at the sample
was used. The instrument was calibrated with mercury
lines or the plasma lines of the laser. The spectrum of the
gas phase was obtained using the Cary multipass acces-
sory and an approximate sample pressure of 300 torr.
The spectrum for the liquid phase was recorded with the
Sam le sealed in a glass capillary in a Miller-Harney
cell.1:The spectrum of the solid phase was obtained by
condensing and annealing the sample on a copper block
in a typical cold cell6 cooled by boiling nitrogen.
Polarization measurements were made by using the
standard Cary accessories.
Frequencies for the Rarnan spectra are expected to be
accurate to *2 cm-' for sharp resolvable bands. For
spectra recorded on the Perkin-Elmer 621, frequencies
should be accurate to *2cm-' for sharp resolvable
bands. Spectra recorded using the Digilab FTS-15B
should have frequencies which are as accurate as the
resolution.
VIBRATIONAL ASSIGNMENT
By using the molecular structure and dipole moment
components determined in a microwave study of
@ Heyden & Son Ltd, 1981
I 1 I 1
2000 I500 1000 500
methyldifluorophosphine by Codding et ul.,' the mole-
cule is expected to exhibit C, symmetry. Therefore, the
assignment presented in this work is based upon the C,
symmetry point group under which the 15 fundamental
vibrational modes are distributed as 9Af+6A".All 15
frequencies are IR- and Raman-active. The A' vibra-
tions will give rise to polarized Raman lines whereas the
A" modes will be depolarized. The plane of symmetry,
which contains the C-P bond, bisects the FPF angle.
Therefore the intermediate moment of inertia (I,) lies
along the axis perpendicular to the plane of symmetry,
while the other principal moments (Ia,I,) lie in the plane
of the molecule. Thus, the IR spectrum of the vapor
phase should exhibit A / C hybrid band contours for the
vibrations which have their dipole change in the sym-
metry plane (A' modes), whereas for the out-of-plane
vibrations (A"),the dipole change would be along the b
axis direction and hence will give rise to B- type band
contours which are expected to have two Q branches
separated by approximately 4.5 cm-'. Although the A,
C or A / C hybrid band contours had clearly discernible
Q branches which were utilized in the assignment of the
A' modes, the B band contours were rather ill-defined.
However, the depolarization ratios from the Raman
spectra made the assignments for the A" modes quite
definite.
JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 45
 J. R. DURIG, A. E. STANLEY AND M. R. JALILIAN

Figure 2. Far-IR spectra of methyldifluorophosphine: (a) gaseous, 80 torr, Res=0.5, 12 c m cell, 1000 scans; (b) gaseous, 300 torr,
Res= 0.25, 12 cm cell, 2000 scans; (c) gaseous, 300 torr, Res = 0.25, 1 m cell, 3000 scans; (d) solid.

C-H stretching modes CH3 deformation modes

The methyldifluorophosphine molecule will have three
C-H stretching vibrations, two of which will belong to
the A' species while the other one belongs to the A"
species. The two bands giving rise to the polarized
Raman lines will be the two in-plane C-H stretching
modes. It is expected that the symmetric mode will be
the lowest frequency. The most intense band in the
Raman spectrum of CH3PF2occurs at 2915 cm-' in the
gas phase and it is polarized. The lower frequency bands
observed in the spectrum of the liquid at 2815,2795 and
2555 cm-' are weak and can be attributed to overtones
of the methyl deformations (Table 1). Only two other
bands have been observed, at 2997 and 2992 cm-', in
the Raman spectrum of the gas phase. The 2992 cm-'
line is polarized and therefore is assigned to
the antisymmetric stretch ( A ' ) and the 2997 cm-'
line is assigned to the antisymmetric stretch of the A"
species.
Of the three CH3 deformational modes (2A'+A")
expected for methyldifluorophosphine, two are
polarized in the Raman effect. The totally symmetric
deformation for CH3PX2 jX= C l, CN, CH3, H) is
found8-" around 1300 cm- . This frequency has been
observed at 1288 cm-' in CH3PClZ8and at 1300 cm-' in
CH3P(CN)2,'0 and therefore the polarized Raman line
observed at 1287 cm-' is assigned to this mode. The two
remaining CH3 deformational frequencies are expected
in the 1400-1430cm-' region. These two bands are
observed at 1417 and 1405 cm-' in the IR spectrum of
the gas phase. The band at 1417 cm1-' corresponds to the
polarized Raman line at 1420 cm- and must arise from
the A' antisymmetric deformational mode, and
obviously the other one must arise from the A" CH3
antisymmetric deformation. This assignment is
comparable with the results obtained for CH3PC128'9
10
and CH3P(CN)2.

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 VIBRATIONAL SPECTRA AND STRUCTURE OF ORGANOPHOSPHOROUS COMPOUNDS

3000 2 500 2000 I500 1000 500 0

Wavenumber (cm-')

Figure 3. Raman spectra of methyldifluorophosphine: (a) gaseous; (b) liquid; (c) solid.

CH3 rocking modes
By comparison with CH3PC12,8'9 CH3POC1~,8
CH3PSCI2,' (CH3)3P,'*and (CH3)2PC1,'3one expects to
find the rocking modes of the CH3PF2 molecules within
the range of 850-900 cm-I. Experimentally, two bands
are observed in this region at 889 and 859 cm-' in the IR
spectrum of the gas phase. The 889cm-' band which
corresponds to the line in the Raman spectrum at the
same frequency is therefore assigned to the in-plane
rocking mode, v5. The 859cm-I band shows an
apparent PQR band contour in the IR spectrum of the
vapor phase but its Raman counterpart at 850 cm-' in
the spectrum of the liquid is depolarized, and therefore
is assigned to the out-of-plane rocking mode, V ~ ZThis
. (687cm-').'" As in the case of CH3PC1z,9 the P-C
assignment is in complete agreement with the ass gn-
ments of the correspondin motions in other methyl-
phosphine derivatives. 8,9,1153
P-C stretching modes
In assigning the C-P stretching fundamental, one can
easily locate it at 701 cm-' in the IR spectrum since it
exhibits a well defined A-type band contour. Addition-
ally, it appears as a strong, polarized line in the Raman
spectrum at 702 ern-'. This frequency correlates well
with those found for the analogous fundamental in the
spectra of CH3PC12 (669 ~ m - * ) * .and ~ CH3P(CN)z

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 J. R. DURIG, A. E. STANLEY AND M. R. JALILIAN

Table 1. Observed frequencies (cm-1) and vibrational assignment of methyldifluorophosphine

Raman Infrared
_ _ _ -
Rel. Rel.
Rel. Int. and Int. and Rel. Rel.
Solid Int. Liquid Depol. Gas Depol. Solid Int. Gas Int. Assignment

3003 R
2995 sh,w 2994 w,dp 2997 w.dp 2995 w 2996 Q W vl0 CH3 antisymmetric stretch ( A ” )
2985 rn 2988 w, p 2992 br w,p w 2992 ctr W v1 CH3 antisymmetric stretch ( A ’ )
2925 R
2910 s 2914 s,p 2915 s, p 291 5 w 2915 Q W v 2 CH3 symmetric stretch ( A ’ )
2900 P
2xv3
2xv11
2xv4
1430 R
1416 m 1417 Q v3 CH3 antisymmetric deformation
(A‘)
1410 sh 2 x v7
1411 R
1405 w 1410 w.dp 1403 m 1405 ctr m v T 1 CH, antisymmetric deformation
1400 P (A“)
1290 1299 R
1283 w 1292 Q m v4 CH3 symmetric deformation ( A ’ )
1279 1277 P
975 Q W
972 w 961 Q W
947 a W
923 0 W
901 R
894 vw 890 w,p 889 W,P 895 S 889 Q W v 5 CH, in-plane rock ( A ’ )
866 vvw 860 sh
870 R
851 vw 850 w,dp 850 S 859 Q S v 1 2 CH, out-of-plane rock ( A ” )
845 P
802 vw 2XV8
825 w 823 R
789 w 798 S 812 Q S v6 PF, symmetric stretch ( A ’ )
755 w 767 S 800 ctr S v13 PF, antisymmetric stretch ( A ” )
727 w 713 R
715 s 709 s,p 702 s,p 71 1 rn 701 Q m v7 PC stretch ( A ’ )
689 P
418 R
404 vw 405 w, p 402 m,p 405 m 405 Q m v8 PF, wag ( A ’ )
390 P
330 R
326 vw 325 w, p 318 wr P 328 s 321 Q vg PF, scissors ( A ’ )
310 P
287 vw 285 w,dp 280br w,dp 288 w 278 ctr vw v I 4 PF2twist ( A ” )
215 vw 192 vw CH3torsion ( A “ )
~ 1 5

111 w 102 W Lattice modes

98 w 75 W
75 w
49 w

stretching vibration occurs at a higher frequency due to
the coupling of the P-C mode with the PF2 symmetric
stretching mode.
Vibrations of the PFr moiety
From an inspection of the IR spectrum of gaseous
CH3PF2 one readily places the PF2 symmetric and
antisymmetric stretching modes at 812 and 800 cm-l,
respectively. It can be seen in Fig. 3 that these two
fundamentals overlap strongly, and without the aid of
Raman depolarization data, the assignment is not easily
made. From the previous work on PF2 containing mole-
c u l e ~ ’ ~it - was
~ ~ expected that the P-F symmetric
stretching mode would occur at a higher frequency than
the P-F antisymmetric stretching vibration. Raman
depolarization measurements easily differentiated
between these two modes and indicated that the higher
frequency line at 812cm-’ is polarized, whereas the
Raman line at 800 cm-’ is depolarized.
With the exception of the torsional motion, there are
only three normal modes remaining to be assigned in the
methyldifluorophosphine. These three vibrations are
the PF2 wagging mode (A’), the PF2 deformational
(scissors) motion (A’) and the PF2 twisting vibration

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 VIBRATIONAL SPECTRA AND STRUCTURE OF ORGANOPHOSPHOROUS COMPOUNDS

(A").The first two motions are expected to show a PQR

structure and the third is expected to be depolarized. It is
not obvious which of the two polarized bands at 405 and
321 cm-' is the wagging and which is the deformation
(scissoring). However, an argument which has been used
previously with molecules such as PF'CN" and
CH3AsHzz0applies here. If we consider PF3, a molecule
with symmetry, the corresponding vibrational
modes are A1 and E which occur near 487 and
344 cm-', respectively." The substitution of a methyl
group for a fluorine atom gives a molecule of C, sym-
metry. The A l vibration becomes the A', PFz wagging
vibration. The degenerate E mode yields the A' scissor-
ing dotion and an A" twisting vibration. This obser- Figure 4. Internal coordinates for methyldifluorophosphine.
vation along with the fact that the scissoring mode in
HPF214*'8is observed at 358 cm-' indicates that the
wagging motion should have the higher frequency. NORMAL COORDINATE CALCULATIONS
Replacement of H in HPFz with a methyl group should
lower the frequency of the scissoring vibration due to the The calculation of the normal coordinates was under-
increased mass. We can then conclude that in C H ~ P F Z , taken in order to investigate the amount of mixing
the PFz wagging mode occurs at 405 cm-' and the between the low-frequency modes and to obtain a more
scissoring mode at 321 ern-.'. It is an easy matter then to complete and well-grounded interpretation of the
assign the depolarized band at 280cm-' to the PFz vibrational spectra of methyldifluorophosphine. The
twisting mode. This assignment for CH3PF2is consistent analysis was made using the Wilson GF-matrix
with the vibrational assignments of the molecules methodz1 and programs written by Schachtschneider."
PF2CN1' and PFzOCH3.'9 The wagging, scissoring and The G matrix was calculated using structural parameters
twisting modes of PFzCN are assigned at 460, 345 and estimated by Codding et al.' from the microwave study.
412 cm-', respectively. For PFz0CH3 these modes are Initial force constants for the P-F stretch, P-C stretch,
assigned at 537, 477 and 372 cm-', respectively. FPF bend and FPC bend were t a k e y p m the published
values for PFzCN by Cox et al. The initial force
constants for the methyl group were taken from the
Internal rotation
work of Snyder and Schachtschneider.z3 The 14 internal
coordinates consisting of the bond lengths and bond
In the far-IR spectrum of the vapor, a weak band is angles shown in Fig. 4 were used as a first step for the
observed at approximately 192 cm-' and is broad with calculations. Symmetrization was accomplished using
no detectable Q branch. The band contour is probably the symmetry coordinates listed in Table 2. The Slo
B-type with at least one associated 'hot band'. No symmetry coordinate has been defined as a zero-co-
reasonable difference band could be found for this ordinate redundancy. The calculated frequencies and
frequency. Additionally in the Raman spectrum of the associated normalized potential energy distribution
solid a weak band is observed at 215 cm-' which could among the symmetry coordinates are listed in Table 3.
either be a two phonon band or the band which cor- Using the modified valence force field shown in Table 4,
responds to the 192cm-I IR band. We believe the
192 cm-' IR band is the methyl torsional mode and the
band maximum is probably the result of the overlap of
the P branch of the fundamental with the R branch of
the first 'hot band'. Table 2. Symmetry coordinates"for CH3PF2
Several attempts were made to observe the torsional A' species
overtone in the Raman spectrum of the gas by utilizing CH3 asyrn. str
very high sensitivity and extremely slow scanning CH3 sym. str.
speeds. A pronounced shoulder was observed on thf CH3 asym. def.
low-frequency side of the PFz wag at 398cm- . CH3 sym. def.
However its intensity and behavior indicated that it was CH3 rock
a 'hot band' of the PFz wag rather than the torsional P-F sym. str.
overtone. P-C str.
Using the frequency for v15 of 192cm-' and the PF2 wag
PF2 def.
potential energy function for a threefold torsional oscil-
CH3 redundancy
lation which can be written as V(a) = ( V3/2) (1+cos
3a) + ( V6/2) (1+ cos 6 a), a valu: for V3,the barrier to
internal rotation, of 223 *10 cm- (1.74 kcal mol-') was s11 r6 - r7 CH3 asyrn. str.
obtained. The reduced moment of inertia constant, F = s12 ff5-ff6 CH3 asym. def.
hz/87rzIr)where I, is the reduced moment of inertia for s13 &-P7 CH3 rock
the internal rotation, utilized in this calculation had a s 1 4 x3-x4 P-F asym. str.
calculated value of 8.325 cm-'. Due to the lack of s16 Y3-Y4 PF2 twist
additional torsional transitions, the VSterm was neglec- a Not normalized.
ted in the barrier calculation.

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 J. R. DURIG, A. E. STANLEY AND M. R. JALILIAN

good agreement since the observed frequencies are

Table 3. Observed IR frequencies, calculated frequencies and lower for CH3PF2 than for PF2CN. Otherwise, the
potential energy distribution"of CH3PF2 values of the force constants are in reasonable
Observed agreement with those found for other molecules with the
(cm-') Calculated Assignment and potential energy distribution PF2 moiety. 14.15.18
A'
2992 2991 CH3 asyrn. str. (100%)
291 5 291 5 CH3 sym. str. (100%)
1417 1413 CH3 asyrn. def. (96%)
DISCUSSION
1292 1292 CH3 sym. def. (91%),P-C str. (9%)
889 880 CH3 rock (56%).PF2syrn. str. (36%) To support the assignment of the symmetric and
81 2 812 PF2 sym. str. (60%). CH3 rock (35%) antisymmetric stretching modes of the PF2 group, a
701 701 P-C str. (73%), PF2 wag (ll%), review will now be made of the assigned frequencies for
CH3 asym. def. (9%) the stretching modes of molecules containing the PCl2 or
405 406 PF2 wag (83%).P-C str. (12%) PF2 moiety. Vibrational assi nments for CH3PC12,"'
321 321 PF2 def. (95%) CF3PCl2? F2PCN,I5PF2H'4z1'and PF20CH319indicate
A" that for the stretching modes there is a shift to lower
2996 2991 CH3 asyrn. str. (100%)
frequencies upon condensation. The antisymmetric PC12
stretchin mode has been observed in CH3PC1z8 at
1405
859
1412
878
CH3 asyrn. def. (96%)
CH3 rock (61%), PF2 asyrn. str. (33%)
F
495 cm- (gas) and 479 cm-' (liquid) in the IR spectrum.
800 791 PF2 asyrn. str. (65%),CH3 rock (33%) Griffiths' has obse:ved the symmetric P F 2 stretching
278 278 PF2 twist (97%) mode at 429cm- (g;s) and 425 cm- (liquid) for
CF3PC12,and 497 cm- (gas) and 487 cm-' (liquid) for
a Contributions of less than 5% are not included.
CH3PC12.Values for the antisymmetric stretching mode
of CF3PC12wFre reported by Griffiths as 526 cm-' (gas)
and 523 cm- (liquid). Cox et ~ 1 . 'reported
~ the sym-
the average difference between the observed and cal- metric stretching mode of the F2PCN molecule at
culated frequencies was found to be 4.0 cm-' (0.4%). 869 cm-' (gas) and 858 cm-' (liquid) in the Raman
In general the force constants associated with the CH3 spectra. The corresponding antisymmetric stretches
stretch ( K r )and CH3 deformation (El2) are comparable were reported at 858 cm-' (gas) and 840 cm-' (liquid).
to those calculated for hydrocarbons. This similarity is For PF2H, the PF2symmetric stretching mode is located
attributed to the purity of these motions. However, the at 852cm-' (gas) and at 822cm-' (solid) while thy
spectral region which contains the CH3 rocking motions antisymmetric stretching vibration shifts from 825 cm-
should be explained in more detail. During the force (gas) to 780 cm-' (solid)." For each of these molecules
constant iterations it was found that very small changes there has been a downward shift in the frequency for the
in the force field have a significant effect of reversing the P-X2 stretching mode upon condensation. To better
assignment of the PF2 stretch and CH3 rocking modes. establish this trend let us consider the vibrational
As expected, the amount of mixing is less in the A' assignments of the PX2 stretching modes in molecules in
symmetry block where the P-F stretch occurs at a all three phases.
higher frequency and the CH3 rock occurs at a lower The PF2 symmetric stretching mode of the PF20CHT
frequency than the corresponding motions in the A" molecule has been observed'' at 829,808 and 788 cm-
block. The value of the force constants for the PF2 in the gas, liquid and solid phases, respectively, while the
scissors, wag and twist are slightly less than those cal- corresponding antisymmetric stretching frequency is at
culated for the similar motions in PF2CN.15 This is in 797, 792 and 779cm-', respectively. In the present
investigation of CH3PF2the PF2 symmetric stretch is at
812,795 and 789 cm-' in the Raman spectra of the gas,
Table 4. Force constants for CH3PF2 liquid and solid, respectively; likewise, the antisym-
metric stretch was observed at 800,769 and 755 cm-'.
Force
constant Group Valuea Plainly, for all these molecules, the PX2 stretching
C-H stretch 4.802
mode undergoes a uniform transition from a high
P-F stretch 4.67 frequency in the gas phase through an intermediate level
C-P stretch 2.969 for the liquid phase, to the lowest frequency in the solid
HCH bend 0.511 state. A similar ob~ervation'~ was made for (CH3)2PCl.
HCP bend 0.451 In this molecule Durig and Saunders13 observed the
CPF bend 1.397 P-Cl stretching mode in the gas phase at 481 cm-' (IR)
FPF bend 0.981 and 485 cm-' (Raman). In the Raman spectrum of the
C-H stretch/C-H stretch 0.045 liquid phase, the band shifted 20 cm-' lower in
P-F stretch/P-F stretch 0.504 frequency. On crystallization, two bands were observed
P-F stretchlFPF bend -0.036 at 551 and 423 cm-' for the out-of phase and in-phase
CPF bend/CPF bend 0.506
-0.033
components of the P-Cl stretching mode while only a
HCP bend/HCP bend
C-P stretch/HCP bend -0.027 small vestige of the original absorption was found. These
observations are strong evidence for some type of
aStretching constants are i n units of rndyne A-'; stretch-bend energy of association involved in the condensed phases.
constants are i n units of rndyne rad-'; bending constants are in These attractions vanish with the vaporization of the
units of rndyne 8, rad-'.
liquid and result in the stretching modes occurring at

50 JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 @ Heyden & Son Ltd, 1981
 VIBRATIONAL SPECTRA AND STRUCTURE OF ORGANOPHOSPHOROUS COMPOUNDS

higher frequencies in the gas phase. It is obvious that

these attractions are stronger in the solid phase than in Table 5. Torsional barriers for some Group IVA and VA
the liquid phase. hydrides and fluorides
Codding et al.' reported the far IR spectrum of Group IVA Group VA
CH3PF2 and assigned the lowest wavenumber vibra- Compound Barrier Ref. Compound Barrier Ref

tions, other than the torsion, at 408 cm-' and 325 cm-' CH3CH3 2.938 24 CH3NH2 1.98 37
The present work shows that the lowest two vibrational CHBCHZF 3.33* 0.05 25-29 CH3NFz 4.17 38
modes, excluding the torsion, are the PF2scissoring and CHjCHF2 3.18 25,27
twisting motions at 328 cm-' and 278 cm-', respec- CH3CF3 3.19 30
tively. Thus the assignment presented in the microwave CH3SiH3 1.7k 0.1 31 CH3PH2 1.959 39
work cannot be correct. CH3SiH2F 1.559 32 CH3PFz 1.74 this
work
The trends for torsional barriers have been CH3SiHF2 1.255 33
established for group IV compounds of the type CH3SiF3 0.93k 0.09 34
CH3MH3,CH3MH2F, CH3MHF2,CH3MF3,where M is CH3GeH3 1.24 35 CH~ASH, 1.48k0.05 40
carbon or silicon and limited data are also available for CH3GeH2F 0.94 36 C H ~ A S F ~1.325*0.08 41
analogous germanium compounds. These barriers are
summarized in Table 5 . These data established that
carbon, the first member in group IV, is unique since the fluorine substitution occurs. There is a decrease in the
initial substitution of fluorine for hydrogen in ethane barrier to rotation in the analogous phosphorous and
increases the barrier to rotation for the methyl group arsenic compounds. The barrier to rotation of
followed by a decrease in the barrier as substitution 2.300 kcal mol-' for CH3PF2 as determined in the
continues. The barrier to rotation in analogous silicon microwave work by Codding et al.' is too high to fit this
and germanium compounds uniformly decreases as trend. The barrier to rotation for CH3PF2as reported
fluorine atoms are added. here is in better agreement with comparisons to analo-
It would not be unusual to see the same trend exhi- gous compounds and trends.
bited for the corresponding compounds of group V (see
Table 5 ) . These results show the same trend for the
group V elements as was observed for the group IV Acknowledgement
elements. Nitrogen is unique in this group with respect The authors gratefully acknowledge the financial support of this study
to the increase in the methyl barrier to rotation as by the National Science Foundation through grant CHE-79-20763.

REFERENCES

1. E. G. Codding, R. A. Creswell and R. H. Schwendeman, Inorg.
Chem. 13,856 (1974).
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Received 4 April 1980
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@ Heyden & Son Ltd, 1981 JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 51