1558
J. R. DTJRIG AND J. B. TURNER
Vibrational Spectra and Structure of Organogermanes. XII.
Normal Vibrations
and Free Rotation in p-Chlorophenylgermane and p-Fluorophenylgermane by J. R. Durig* and J. B. Turnerlb Department of Chemistry, Unizersity of South Carolina, Columbia, South Carolina 29208
(Received July 12, 1971)
Publication costs borne completely by The Journal of Physical Chemistry
The infrared spectra of liquid and gaseous p-chlorophenylgermane and p-fluorophenylgermane have been recorded from 4000 to 200 cm-l. The Raman spectra of the liquids have also been recorded, and depolarization values have been measured. The vapor-phase spectra show that the germyl group is freely rotating for these molecules. Thus, the local symmetry of the phenyl ring can be considered as C, and the phenyl vibrations have been assigned according to this symmetry. The effective symmetry of the GeHa group is essentially Ca0. All spectra have been interpreted in detail, and the fundamental vibrations have been assigned based on previous assignments of disubstituted benzene and its isotopic derivatives, depolarization ratios, and vapor-phase infrared band contours. The free rotation of the germyl group shows that the sixfold barrier to internal rotation around the C-Ge bond is negligibly small.
Introduction Recently we have investigated2 the spectra of phenylgermane and its deuterated analogs, in which free rotation of the germyl group was observed. In continuing our investigations of organogermanium compounds, we have recorded the infrared, far-infrared, and Raman spectra of p-fluorophenylgermane and p-chlorophenylgermane. No vibrational data have been previously reported for either of these molecules. The present study was undertaken to examine the effect of a halogen in the para position upon the vibrational-rotational fine structure for the "degenerate" GeH3 fundamentals. Therefore, we have analyzed the vibrational spectra for these two molecules in detail, and discuss the proposed assignment with its ramifications.
Experimental Section The preparation of p-chlorophenylgermane was carried out in the following way. A 250-ml three-necked flask, containing 2.5 g of Grignard grade magnesium and a magnetic stir bar, was fitted with a water-cooled condenser, a 100-ml dropping funnel, and a thermometer. Approximately 20 g of 1-bromo-4-chlorobenzene was dissolved in 100 ml of anhydrous diethyl ether and added slowly to the flask containing the magnesium. Reaction was not spontaneous but could be initiated by heating. Following complete addition at reduced temperature, the mixture was refluxed for 1hr and then cooled. Excess magnesium was removed and the mixture placed in a dropping funnel. This funnel was connected to a three-necked 500-ml flask equipped with a magnetic stirrer, heating mantle, condenser, and thermometer. Into this flask, 150 ml of anhydrous ether containing 25 ml (approximately 46 g) of GeC14 was transferred. Proper care was exercised to preclude any contact of either reactant with moisture. The quantity The Journal of Physical Chemistry, Val. 76, No. 11, 1972
of GeC14 was chosen to be appreciably in excess and ether was used to maintain a low reflux temperature to favor monosubstitution on the GeC14. The p-chlorophenylmagnesium bromide in ether was added dropwise to the GeC14 at 0" with constant stirring, and a dense white precipitate formed; it was necessary to stir vigorously. The dropwise addition of p-chlorophenylmagnesium bromide solution was complicated by the settling of the relatively insoluble Grignard. After the addition was complete, the reaction was refluxed for 70 hr. Solid material was removed by filtering through a mediumporosity sintered-glass filtering funnel and the residue washed well with ether. The filtrate was placed in a 250-ml flask and the ether was distilled from the reaction mixture. When the temperature of the distilling flask began to rise above 35", the flask was cooled, the pressure was lowered, and all materials which were volatile a t 10 Torr and up to 40" were removed. The remaining material was a slightly yellow solid which hydrolyzed readily upon exposure to air. This solid was immediately dissolved in anhydrous ether and placed in a 25-ml dropping funnel. No problems of solubility were incurred if proper precautions had been taken to prevent hydrolyses. For complete reduction of the amount of p-chlorophenylgermanium trichloride produced by 1 0 0 ~ oyield, 2.7 g of LiAlH4 would be needed. Since in all probability a mixture of RGeCla, R2GeC12, and R3GeCl was present, 2.5 g was used and expected to be a considerable excess, which was found to be the case. The reduction was carried out in a (1) (a) For part XI, see Spectrochim, Acta, Part A, 27, 1623 (1971); (b) talcen from a thesis submitted by J. B. T. in partial fulfillment of the requirements for the Ph.D. degree, University of South Carolina, Jan 1970. (2) J. R. Durig, C. W. Sink, and J. B. Turner, J. Chem. Phys., 49, 3422 (1968).
1559
VIBRATIONALSPECTRA AND STRUCTURE OF ORGANOGERMANES
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Figure 1. (A) Mid-infrared spectrum of p-fluorophenylgermane.
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1MX)
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FREQUENCY (CM')
(B) Raman spectrum of p-fluorophenylgermane.
manner analogous to the (C6H&GeH2 p r e p a r a t i ~ n . ~ The sample of p-chlorophenylgermane was collected a t 8 Torr and 60". Any attempt to collect the other substituted germanes was futile. The reaction mixture turned yellow, then red as thermal decomposition and polymerization occurred. The yield was extremely low, approximately 1 ml. The sample of p-fluorophenylgermane was prepared in a similar manner. The Grignard reaction was easier to initiate with pbromofluorobenzene than with p-bromochlorobenzene, and the final product (p-fluorophenylgermane) was collected a t 6 Torr and 50". These compounds have fairly high boiling points and degraded on those gas chromatographic columns tried; i.e., Carbowax, UCON, diisodecyl phthalate. When the infrared spectra were taken, it was apparent that only the GeH3 substituent was present, with no spectroscopically observed GeHz or GeH moiety. The samples showed a very weak Raman line at 998 cm-l which is the most intense band other than the GeH stretch in the Raman of monosubstituted phenylgermanes. From the intensity of this line it can be assumed with confidence that the trace of phenylgermane would not contribute any other observable lines, and these two compounds were thus examined as prepared. The infrared spectra between 4000 and 200 cm-l were recorded with a Perkin-Elmer Model 621 spectro-
photometer and between 500 and 33 cm-' with a Beckman IR-11 spectrophotometer. Both instruments were purged with dry air and calibrated with standard gases.4 For studies of the vapor phase, 20em cells with cesium iodide windows were used in the mid-infrared, whereas a Beckman 10-m variable-path cell with polyethylene windows was used for recording the far-infrared spectra. The infrared spectra of the liquids were obtained as a capillary film between cesium iodide plates. The infrared spectrum of liquid pfluorophenylgermane is shown in Figure 1A and portions of the vapor spectrum are shown in Figure 2. The corresponding infrared spectra of liquid and gaseous pchlorophenylgermane are shown in Figures 3A and 4, respectively. The observed frequencies are listed5 in Tables I and 11. (3) J. R. Durig, J. B. Turner, B. M.Gibson, and C. W.Sink, J . Mol. Struct., 4, 79 (1969). (4) (a) "IUPAC, Tables of Wavenumbers for the Calibration of
Infrared Spectrometers," Butterworths, Washington, D. C., 1961; (b) R. T. Hall and J. M.Dowling, J . Chem. Phys., 47, 2454 (1967); 52, 1161 (1970). (5) Listings of all of the observed bands, along with the frequencies for the. individual branches, will appear immediately following this article in the microfilm edition of this volume of the journal. Single copies may be obtained from the Business Operations Office, Books and Journals Division, American Chemical Society, 1155 Sixteenth Street, N.W., Washington, D. C. 20036, by referring to code number JPC-72-1558. Remit check or money order for $3.00 for photocopy or $2.00 for microfiche. The Journal of Physical Chemistry, Vol. 76, N o . 11, 1978
1560
J. R. DURIQAND J. B. TURNER I
II
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(CM"J
900 FREQUENCY ICM')
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Figure 2. (A) Gas-phase infrared spectrum showing the GeHs stretching region of p-fluorophenylgermane. (€3) Gas-phase infrared spectrum showing the GeHa deformation region of p-fluorophenylgermane.
Vibrational Assignment Phenyl Modes. The vapor-phase spectra of p-fluoro-
berg's notation.* A pictorial representation of the motions of the phenyl ring has been presented by Schererg for the complete series of chlorinated benzenes, and approximate descriptions of these motions are listed in Table 111. This table includes the numbering system employed in this paper and corresponding numbers used in the p-dihalobenzene paper^.^*'^," The assignment of fundamental frequencies is facilitated by comparison with the assignments for phenylgermane2 and reference to the spectral data for the symmetrical and unsymmetrical dihalogenoben~enes,'~~~'~ with particular reference t o those unsymmetrical dihalogenobenzenes, p-bromofluorobenzene and p-bromochlorobenzene. These two, from the standpoint of
phenylgermane and p-chlorophenylgermane exhibit fine structure on those bands known to be characteristic of the germy1 group. This feature in the spectra is indicative of free or nearly free internal rotation about the Ge-C bond, as explained in the final section of this paper. The effective symmetry of the phenyl group is then Czv,with the 30 fundamental vibrations of the substituted benzene ring factoring into llal, 3az, 10b1, and 6bz symmetry. These fundatmentab are described by an adaptation of Whiffen's? notation for para disubstituted benzenes renumbered to correspond to Herz-
(6) R. C. Hawes, K. P. George, D. C. Nelson, and R. Beckwith, Anal. Chem., 38, 1842 (1966). (7) A. Stojiljkovic and D. H. Whiffen, Spectrochim. Acta, 12, 47 (1958). (8) G. H;;zberg, "Infrared and Raman Spectra of Polyatomic Molecules, Van Nostrand, Princeton, N. J., 1945, p 271. (9) J. R.Scherer, Spectrochim. Acta, 19, 601 (1963); 21, 321 (1965); Spectrochim. Acta, Part A , 24, 747 (1968). (10) A. Stojiljkovic and D. H. Whiffen, Spectrochim. Acta, 12, 57 (1958). (11) P. N. Gates, K. Radcliffe, and D. Steele, Spectrochim. Acta, Part A , 25, 507 (1968).
The Raman spectra of the liquid samples sealed in glass capillaries were recorded with a Cary Model 81 spectrophotometer equipped with a Spectraphysics Model 125 helium-neon laser. The instrument was calibrated with emission lines from a neon lamp over the spectral range 0-4000 cm-l. Qualitative depolarization values were obtained in the manner described by Hawes, et aL6 The frequencies of the observed lines are listed5 in Tables I and 11, and the spectra are shown in Figures 1B and 3B. All listed frequencies are believed to be accurate to l cm-l for all sharp bands.
The Journal of Phgsical Chemistrg, Vol. 7%,No. 11, 1072
1561
VIBRATIONAL SPECTRA AND STRUCTURE OF ORGANOOERMANES Table I11 : Vibrational Fundamentals for p-Fluorophenylgermane and p-Chlorophenylgermanea c
Raman
3065 3065 1590 (ms, dp) 1498 (9, P ) 1230 (vs, p) 1162 (ms, p ) 1086 (ms, p )
Infrared
3065 (w) 3065 (w) 1595 (s) 1498 (5, A) 1239 (s, A) 1163 (m, A) 1089 (m) 1015 (w) 817 593 (m) 267 (m)
C~-CBH~-G~HP-----. Infrared Raman
3085 (ms, p) 3056 (s, p ) 1588 (m, dp) 1480 (w) 1181 (w, P) 1101 (w, P) HI79 (9, P)
730 (vs, P) 492 (vw) 246 (s, P)
398 (w)
3072 (mw, dp) 1590 (ms, dp) 1305 (w) 1270 (vw) 1065 (m) 632 (ms, dp) 287 (ms, dp)
3106 (w) 3079 (w) 1595 (s, B) 1388 (m) 1306 (w) 1259 (w) 1068 (m) 632 (w) 420 (w) 289 (m)
493 (vw) 323 (vw,dp) 228 (w)
1015 (w, A) 731 (m, A) 492 (vw) 246 (m)
(813)a (410)d
3044 (w, dp) 1588 (m, dp) 1301 (w, dp) ( 1079)d 628 (m, dp) (418)d 249 (vw)
Species BI 3098 (w) 3040 (m) 1593 (m) 1381 (ms) 1300 (m) 1240 (w) 630 (vw)
Species Bz 926 (vw)
936 (m)
(812)d
1593 (m) 1493 (s, A) 1180 (w) 1098 (m) 1083 (m, A)
Species A2 960 (vvw)
947 (m) (813)d
Species AI 3082 (w)
(812)d 672 (w) 485 (vw) 315 (m, C) 227 (w)
580 (m, b ) 594 (m) 834 (vs, A) 874 (vs) 2073 (vs) 2085 (vs, A)
312 (vw) 198 (vw)
584 (vw) 822 (ms, P) 880 (vs, dp) 2077 (vs, p)
708 (m) 465 (m) 316 (m) GeH3 Vibrations 580 (ms, B) 594 (9) 834 (vs, A) 878 (vs) 2074 (vs) 2088 (vs, A)
Assign no.
1 2 3 4
Assignb no.
Descriptionc
6 7
1 18 2 19 3 20 4
8 9 10 11
21 5 22 6
C-H stretch C-H stretch C-C stretch C-H bend (60%), C-C stretch (40%) C-H bend (in plane) Ring (70%), C-X stretch (30%) Ring (50%), C-X stretch (30%), C-H bend (20%) Ring (60%), C-H bend (25%) C-C-C (55%), C-X stretch (45%) C-X stretch (70%), ring Ring, C-X stretch (30%)
12 13 14
16 7 17
C-H (out of plane) (C-H (out of plane)) Ring deformation
15 16 17 18 19 20 21 22 23 24
11 23 12 24 13 25 26 14 15 27
C-H stretch C-H stretch C-C stretch C-C stretch (50%), C-H bend (50%) C-H (in plane) Ring C-H bend (50’%), ring (36%) C-C-C (in plane) C-X (in plane) C-X (in plane)
25 26 27 28 29 30
28 9 29 10 30
5
8
C-H (out of plane) C-H (out of plane) Ring deformation Ring deformation Ring C-X bend In-plane GeH3 rock Out-of-plane GeH3 rock Sym GeH3 deformation Antisym GeHs Antisym GeHs stretch Symmetric GeH3 stretch
Abbreviations used: m, medium; s, strong; w, weak; v, very; A, B, and C, individual band type; p and dp, polarized and depolarized. b Used in p-dihalobenzenes. The approximate descriptions were taken from ref. 8. d Estimated, not observed. a
mass, should have motions very similar to the phenyl motions of p-fluorophenylgermane and p-chlorophenylgermane, respectively. Band contours obtained from vapor-phase infrared spectra considered with polarization data from the Raman spectra further simplify assignments. All species are Raman active, and all except the az modes are infrared active. The a1 species give rise to polarized Raman lines urith A-type infrared vapor-phase contours. The bl and bz modes should give rise to B-. and C-type infrared bands, respectively.
The majority of the fundamentals are readily assigned. Only those requiring some explanation will be discussed, such as VI) V Z , v l j , and v16, the symmetric and antisymmetric C-H stretching modes. In p-bromofluorobenzene, the two symmetric stretching motions are assigned a t 3007 and 3066, whereas the antisymmetric stretching C-H motions are located at 3115 and 3007 cm-l. In p-fluorophenylgermane, the Raman line at 3065 em-l can be shown by polarization measurements to contain both a polarized and a depolarized The Journal of Physical Chemistry, Vol. 76, No. 11, 197.9
J. R. DURIGAND J. B. TURNER
1562
5-
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Figure 3.
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(A) Liquid-phase mid-infrared spectrum of p-chlorophenylgermane. (B) Raman spectrum of p-chlorophenylgermane.
component, which are centered a t 3065 and 3072 cm-l, respectively. Since no other polarized line or A-type infrared band occurs in this region, vl and v2 are assumed to be coincident and fall at 3065 cm-l. The two bl modes, VISand V16, are assigned to the infrared gas-phase band a t 3106 cm-' and the depolarized Raman line a t 3072 cm-l. I n p-chlorophenylgermane, the infrared band a t 3098 cm-' is assigned to bl mode V15. T h e intense Raman line a t 3056 cm-' has shoulders centered a t 3085 and 3045 cm-I. The shoulder at 3085 cm-l proves to be polarized, whereas the 3045-cm-1 band becomes much more distinct and is obviously depolarized. The a1 modes, v1 and v2, are assigned to bands at 3085 and 3056 cm-l, whereas the bl mode, v16, is assigned to the 3044-cm-l band. The C-C stretching motions of a1 and bl symmetry, v3 and v17, are, in the present case as in the almost isobaric dihalogenobenzene analogs, coincident at 1588 cm-I. in p-chlorophenylgermane and 1587 cm-l in p-fluorophenylgermane. These Raman lines are depolarized. The remaining C-C stretching modes are strongly coupled with the C-H bending modes. They are derived from the degenerate 1485- and 1035-cm-1 bands in benzene, and one component of the higher frequency band, v4, does not appreciably change fpequency with substitution. This falls a t 1498 cm-l in p-fluorophenylgermane and 1480 cm-l in p-chlorophenylThe Journal of Physical Chemistry, Vol. 76, N o . 11, 197%
germane and is made up of approximately 40% C-C stretch and 60% C-H bend. The other component, VIE, is lowered because the substitution has reduced the percentage of the C-H bending participation (50%) in the normal coordinate. In p-fluorophenylgermane the bl mode, VB, is assigned to the 1390-cm-' infrared band and in p-chlorophenylgermane to the band a t 1379 cm-l; neither band is observed in the Raman spectrum. The assignments for v8 and vZ1 are made and correspond with those for similar molecules. The spectra in the spectral region expected for these fundamentals require close attention. The al mode, vs, characteristically occurs near 1000 and is frequently not seen in the Raman spectrum; such is the present case. In the spectrum of p-fluorophenylgermane, the infrared band at 1016 cm-', like the corresponding band at 1015 cm-I in the spectrum of p-chlorophenylgermane, has no Raman counterpart. These are therefore assigned to vs. The bl mode, v z l , generally occurs near 1100 cm-I and also is not usually observed in the Raman effect. I n p-fluorophenylgermane, there is a band at 1088 cm-l, but it has a counterpart in the Raman spectrum which is polarized. It is moderately strong and more satisfactorily assigned to the a1 mode, v7. The bl mode, vz1, is therefore unobserved. Similarly, vs is assigned to the infrared band at 1015 cm-l for p-chlorophenylgermane. Also, for p-chlorophenylgermane the 1098-
1563
SPMOIW A AND STRTTCTTJRE OF ORGANOGERMANES VIBRATIONAL
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Figure 4. (A) Gas-phase infrared spectrum showing the GeH3 stretching region of p-chlorophenylgermane. (B) Gas-phase infrared spectrum showing the GeH3 deformation of p-chlorophenylgermane. (C) Gas-phase infrared spectrum showing the GeHs rocking region of p-chlorophenylgermane.
cm-' infrared band has a polarized Raman counterpart and is assigned as the ai mode, V6. The bl mode, VZI, again is unobserved. The a2 modes, V13 and V14, usually are weak or unobserved, and these molecules present no exceptions. Only v14 in p-fluorophenylgermane is observed at 410 cm-l. The a2 mode, v12, is easily assigned to the 947cm-' band in p-fluorophenylgermane and the 960-cm-l band in p-chlorophenylgermane. The vibrational modes, vl0 and v11, in p-chlorophenylgermane are assigned to bands at 492 and 246 om-', respectively. In the p-dihalophenylgermanes, VIO plus v7 produces moderately intense infrared bands. This combination is observed in the spectrum of p-chlorophenylgermanc at 1575 cm-', leading to further con-
fidence in the assignment. I n p-fluorophenylgermane, vlo and V U are assigBed t o bands at 592 and 268 cm-l, respectively. The combination of v10 plus v7 is found a t 1678 cm-l for p-fluorophenylgermane. The C-H out-of-plane deformations, v25 and v12, can be readily assigned as 936 and 926 cm-' for v 2 j and 960 and 947 cm-l for vI2 for p-chlorophenylgermane and pfluorophenylgermane, respectively. Both V13 and vzo fall in the region of the spectrum where the strong GeHs deformation occurs, Thus, one can only assume that they fall near 812 cm-1 and are obscured by the GeHs motion. The out-of-plane ring motion, v29, and the C-X bend, v30, for p-chlorophenylgermane should lie near 300 and 100 cm-', respectively. The infrared band at 316 cm-l The Journal of Physical Chemistry, Vol. 76, No. 11, 1978
1564
J. R. DURIGAND J. B. TURNER
is assigned to VZB. There is not a band around 100 em-', but there is a weak band at 198 cm-l which is tentatively assigned as v30. In p-fluorophenylgermane, vZg is assigned to the band at 323 cm-l, and again there is a weak band at 228 cm-l which is tentatively assigned as v30.
GeH3 Motions. Since the GeH3 group is freely roThe eight vitating, its symmetry is essentially brations are divided into three degenerate vibrations of species e and two nondegenerate vibrations of species a. The symmetric GeH3 stretching vibration is readily assigned to the polarized Raman line at 2078 cm-l in pfluorophenylgermane, which corresponds to a liquidphase infrared band centered at 2077 cm-l. I n pchlorophenylgermane, the Raman line is centered at 2078 cm-l. These Raman lines are symmetrical, with no shoulder apparent on the high wave number side. Thus, the doubly degenerate antisymmetric GeH3 stretching motion appears to be degenerate with the symmetric mode. The symmetric deformation is readily assigned to the polarized Raman line a t 822 cm-I in p-chlorophenylgermane and also occurs a t 822 cm-1 in the infrared spectrum of the liquid. This vibration is observed at 821 cm-I in the Raman effect (826 cm-l in the infrared) for p-fluorophenylgermane. These values agree very well with the assignment for the corresponding motions for the phenylgermane molecule. The in-plane rocking mode is assigned to the weak Raman line a t 584 cm-l in p-chlorophenylgermane, whereas the out-of-plane rocking motion is assigned to the strong liquid phase infrared band a t 591 ern-'. I n p-fluorophenylgermane neither band appears in the Raman spectrum, but two bands are found in the infrared spectrum, The in-plane rocking mode occurs a t 587.5 cm-I and the out-of-plane rock at 593 em-'. The analysis of the gas-phase spectra for this region for both molecules is not clear. There appears to be a B-type band with other bands overlapping it on the high wave number side. I n p-chlorophenylgermane, the B band center of 580.7 cm-l in the infrared spectrum is in good agreement with the 584-cm-l Raman line. The stronger Raman line at 594 cm-1 corresponds to the infrared frequency at 591 em-'. In pfluorophenylgermane, there is a further complication in that v10 occurs a t 592 cm-1 in the Raman effect and is probably contributing to the complexity of the gas-phase spectrum in this region. The center of the B-type band at 580 cm-1 is assigned to the in-plane rocking mode, The out-of-plane rocking mode is then assigned to the 594-cm-1 gas-phase infrared band, which is strongly overlapped by V I O . The approximate rotational constants for p-chlorophenylgermane and p-fluorophenylgermane have been calculated using microwave results of compounds containing Ge-H bonds,l2 Ge-C'a bonds,l3 and other bond lengths from Keidel and Bauer.14 The valence angles
c~,.
The Journal of Physical Chemistry, Vol. 76, No. 11, 1978
about the germanium atom were taken as tetrahedral and all other angles as 120". The values obtained for p-fluorophenylgermane were A = 0.178 cm-l, B = 0.0203 cm-l, C = 0.183 cm-l; for p-chlorophenylgermane A = 0.178 cm-l, B = 0.0146 em-', C = 0.0150 cm-l. These are so small that no fine structure from molecular rotation can be expected in the vaporphase infrared spectra. All the infrared bands attributed to the antisymmetric modes of the gerniyl group exhibit clearly resolved fine structure. The subbands of the antisymmetric stretching and deformational bands show an alternation of intensity strong, weak, weak, which is characteristic of perpendicular vibrations of molecules having a threefold symmetry axis. The rocking mode for p-chlorophenylgermane also shows erratic fine structure, which was not observed in the original vibrational study of phenylgermane.2 HoweveP, in a more recent infrared study15 of phenylsilane and phenylgermane, some fine structure was observed on the rocking modes also. A similar erratic pattern was observed. Fleming and BanwelllBshowed that as the energy difference of the two interacting modes increases, the net effect upon the fine structure increases until band contours for noninteracting vibrational species should be observed. Thus, the erratic fine structure for the rocking modes of p-chloro- and p-fluorophenylgermanes results presumably because the in-plane and out-of-plane motions, though not coincident, overlap sufficiently to thereby give the rotational fine structure of the region. The deviation from the strong-weak-weak alternation is most pronounced on the rocking motions which are split by approximately 14 cm-l. Thus, the rotational fine structure for the perpendicular vibrations of the germy1 moiety must be due to the nearly free rotation of the GeHa group about the Ge-C axis, since the spacing between successive subbands is more than an order of magnitude greater than that required for rotation of the entire molecule. The fine structure is consistent with a barrier of a few calories and is probably in the range of 10-20 cal. The frequencies of the Q branches of the stretching modes are listed" in Tables I V and V, with assignments based on the pattern of relative intensities. The K = 0 subband and the subbands corresponding to multiples of three are relatively strong. Also, the member of a pair of weak bands nearer the band center should be stronger than the adjacent one.17 The rotational (12) G. R. Wilkinson and M. K. Wilson, J. Chem. Phys., 44, 3867 (1966). (13) v. wT.Laurie, J. Chem. Phys., 30, 1210 (1959). (14) F. A. Keidel and S. H. Bauer, J. C h m . Phys., 25, 1218 (1957). (15) J. R. Durig, C. W. Sink, and J. B. Turner, Spectrochim. Acta, Part A, 25, 629 (1969). (16) J. W. Fleming and C. N. Banwell, J. Mol. Spectrosc., 31, 318 (1969). (17) G. Herzberg, ref 8, p 425.
1565
RAMAN SPECTRA O F MOLTENALKALIMETAL CARBONATES structure on the deformation and rocking modes is so perturbed as to preclude any attempt to analyze it other than to reiterate that this is evidence for free rotation of the germy1 group. An average of the distance between unperturbed subbands was taken in order to calculate the Coriolis coupling t for the antisymmetric deformation. The average spacing proved to be 6.3 cm-l in both molecules. Since the average spacing of the Q branches of each of these bands is equal to [2A'(1 - - (B' C')],18,19 the Coriolis coupling constant for the antisymmetric modes can be calculated. For the antisymmetric stretching mode, it is -0.019 for p-fluorophenylgermane and ,-0.014 for p-chlorophenylgermane. For the antisymmetric deformation modes, is -0.168 for p-fluorophenylgermane and -0.171 for p-chlorophenylgermane. The frequencies of the Q branches of the degenerate GeH stretching fundamental were found to fit by a least squares the following equations
(r)
vosub
=
2075.9
f
r)
+
5.69K - 0.02K2
vosub
=
2076.11
f
5.65K
- 0.01K2
for p-fluorophenylgermane and p-chlorophenylgermane, respectively. The band centers were calculated to be 2073.2 and 2074.4 cm-l, respectively. The symmetric stretching frequencies taken from the gas-phase spectra were 2085.2 and 2088.5 em-l, respectively; thus the degenerate antisymmetric and symmetric stretching modes are very nearly degenerate. In conclusion, the molecules p-chlorophenylgermane and p-fluorophenylgermane can be said to possess an extremely small barrier to internal rotation and, therefore, there is essentially "free rotation" about the Ge-C bond at room temperature.
Acknowledgment. The authors gratefully acknowledge the financial support given this work by the National Science Foundation under Grant No. GP20723. (18) C. V. Stephenson, W. C. Coburn, Jr., and W. 5. Wilcox, Spectrochim. Acta, 17, 933 (1961). (19) D. H. Whiffen, J . Chem. Sac., 1350 (1956).
Raman Spectra of Molten Alkali Metal Carbonates1
by J. E. Bates, M. H. Brooker, A. S. Quist, and G. E. Boyd* Oak Ridge National Laboratory, Oak Ridge, Tennessee 17810 (Received December g1, 1971) Publication costs assisted by the Oak Ridge National Laboratory
Raman spectra of molten Lid303 and LizCOrLiCl, LizCOa-CaCO3, NazCO3-NaC1, and KzCO3-KCl eutectic mixtures were measured over the frequency interval from 150 to 2000 cm-l. Raman and infrared spectra at 25' of saturated aqueous solutions of NazC03 and KzCOs were recorded, and Raman spectra of the crystalline Li~C03,NazCOa, and K&03 were obtained from 25 to 692". The Raman forbidden Dah vz(Az") mode of carbonate ion was observed at ca. 880 cm-I, and the 4 E ' ) mode was split in the molten salt spectra. The v3 mode also exhibited two components in the aqueous solution spectra, and the frequencies of the Raman components were noncoincident with those in the infrared.
'
Introduction The relatively high melting points and thermal instability of the alkali metal and alkaline earth carbonates account for the fact that a single, recent paper by Maroni and Cairnsza is the only published report of the Raman spectra of COa2- ion in carbonate melts.2b Techniques developed in this l a b ~ r a t o r y ~for - ~ measuring Raman spectra of corrosive fluoride containing melts a t temperatures to 800" have permitted us to undertake an extensive investigation of molten carbonates. A more complete characterization of the physical properties of molten carbonates is of practical impor-
tance in view of the potential use of these materials for removing sulfur dioxide pollutants from stack emis(1) Research sponsored by the U. S. Atomic Energy Commission under contract with the Union Carbide Corporation. (2) (a) V. A. Maroni and E. J. Cairns, J . Chem. Phys., 52, 4915 (1970). (b) The Raman spectrum of carbonate ion dissolved in molten LiF-NaF-KF has been reported: F. L.Whiting, G. Mamantov, G. M. Begun, and J. P. Young, Inorg. Chim. Acta, 5 , 260 (1971). (3! (a) A. S. Quist, A p p l . Spectrosc., 2 5 , 80 (1971); (b) A. S. Quist, mbmd., 2 5 , 82 (1971). (4) A. S. Quist, J. B. Bates, and G. E. Boyd, J . Chem. Phys., 54, 4896 (1971). ( 5 ) A. 5 . Quist, J. B. Bates, and G. E. Boyd, J . Phys. Chem., 76, 78 (1972). The Journal of Physical Chemistry, Val. 76, No. 11, 197.2
