CHAPTER 15

Organosilicon
Compounds

15-1.
THE - S i H j GROUP

15-1.1. The SIH, Stretchings

Bellamy [1] has correlated the — SÎH3 stretching modes of monoalkylsilanes
(R—SiHg) t o a strong IR b a n d in t h e region of 2153-2142 cm~\ See Table
15-1. The same vibrational modes for m o n o a r o m a t i c silanes v^ere found in
the region of 2157-2152 cm"^ [1]. In t h e majority of cases, t h e frequencies
of t h e antisymmetric a n d symmetric — SiHg modes are so close as t o be

Table 15-1.
The Group Frequencies of SiHj Moieties (cm~^)

IR Reference

The SiHj Stretchings:

R-SiH3 2153-2142 s 1,22,25
Ar-SiH3 2157-2152 s 1,25
-C=C-SiH3 2190-2170 s 1

The S i H 3 Deformations:
947-930 1,2,22,25
930-910
The S i H 3 Rocking:
720-680 1,2

251
252 Chapter 1 5 : Organosilicon Compounds

indistinguishable. Although it was suggested that the presence of a con-

jugated triple bond with the — SiH3 group can split the near-coincidence of
the antisymmetric and the symmetric — SiHg stretchings, as in the case of
1,2-disilyl acetylene [1] (VasiSiHs): 2190 c m - \ v,(Sin^: 2170 cm"^), the IR
study on silylacetylene ( H s S i — C = C — H ) by Ebsworth et al. [2] indicates
that the antisymmetric and symmetric — SiHg modes are stiU superimposed
for this silicon c o m p o u n d . The antisymmetric and symmetric SiHg stretching
frequencies are expected to be considerably closer together than the com-
parable CH3 frequencies because of the heavier mass of the sihcon a t o m .
The same is true for SiH2 stretching frequencies [11].

15-1.2. The SiHj Deformations

By analogy with the —CH3 deformations near 1460 cm"^ and 1 3 7 0 c m " \
the — SiH3 deformations exhibit strong IR bands in the ranges of 947-930
cm"^ and 930-910 cm"^ that can be attributed to the —SiH3 deformations
[1,25]. For example, the antisymmetric a n d symmetric —SiH3 deforma-
tions of silylacetylene were observed at 946 and 935 c m " \ respectively [2].
The — SiH3 rocking mode has been correlated with an IR band in a region
between 720 and 680 c m " ^ The SiH3 rocking m o d e of silylacetylene was
assigned to the strong IR band at 666 c m " ^

15-2.
THE -SiH2 GROUP
Similar to those of the — CH2— moiety, the vibrations of a — SiH2—
moiety are approximated as stretchings, scissoring, wagging, twisting, and
rocking modes. The earher data on the IR frequencies of — SiH2— moieties
have been discussed by Behamy [1]. More recently, the vibrational spectra
of dimethylsilane [4], silacyclopentane [7], methyl methylsilyl sulfide [8],
methyl methylsilyl ether [9], and ethyl methyl silane [10] have been
reported. A summary of the group frequencies of the — SiH2— moiety is
shown in Table 15-2.

15-2.1. -SÎH2-Stretchings
Although the antisymmetric — SiH2— stretching mode of gas-phase sila-
cyclopentane was observed by Durig a n d Wilis [7] using the IR technique to
15-2. The - S i H 2 - Group 253

Table 15-2.
The Group Frequencies of —SiHj— Moieties (cm"^)

SiH2 Stretching cm ^ IR R Reference

R-SiH2-R 2138-2117 s 1,4,5,25

SiH2(CH2)4 (ring) 2149 s vs, ρ 7
Ar-SiHj-Ar 2147-2130 s 25
Ph-SiH2-Ph 2139 vs m, ρ 3a, 18
M e - S i H 2 - S i H 2 - Me 2126 vs vs, ρ 4
Me-SiH2-X 2200-2140 6
(X = Me, F, CI, Br, I)

SiH2 Scissors SiH2 Wag SiH2 Twist SiH2 Rock

SiH2 Deformations IR : s, R : w IR : s, R : w IR:s, R:w IR:s, R:w Reference

R-SiH2-R 950-930 900-840 690-560 540-480 1,4,5,25

Ar-SiH2-Ar 940-928 870-843 25
Me-SiH2-X 980-940 955-875 740-630 520-460 6
SiH2(CH2)4 (ring) 955 885 575 456 7

be at 2151.8 c m " \ this IR b a n d is n o t found in hquid-phase silacyclopentane.

As a matter of fact, only one — SÎH2— b a n d is reported in m a n y instances
for hquid samples, a n d only the symmetric — SiH2— stretching m o d e was
found. While the IR intensity of the SiH2— b a n d appears t o be quite
strong, the polarized R a m a n b a n d assignable t o the SiH2— stretching m o d e
exhibits intensity varying from medium t o very strong.
The earher studies indicate that the — SiH2— stretching modes of dialkyl-
silanes ( R - S i H 2 - R ) are located in the region of 2138-2117 cm"^ [1, 4, 25].
The presence of a second Si a t o m on the — SiH2— group does not cause a
significant shift in the — SiH2— stretching frequencies, as illustrated by the
vibrational spectra of dimethyldisilane (CH3SiH2SiH2CH3), which exhibit a
distinct vibrational b a n d at 2126 cm"^ (IR : vs, R : vs, p) in the hquid phase
[4]. T h e substitution of the alkyl groups by t w o aryl groups appears t o
increase the — SiH2— stretching frequencies slightly, and the — SiH2—
stretching frequencies of diarylsilanes (Ar—SiH2—Ar) are found in a
region of 2147-2130 cm"^ [25]. F o r example, the IR spectrum of diphenyl-
silane (3a) exhibits a strong b a n d at 2139 c m " ^ that can be attributed
to the — SiH2— stretching m o d e . T h e relative R a m a n intensity of the
—SiH2— stretching appears t o be polarized a n d of medium intensity.
Halogenation o n the Si a t o m induces a significant shift of the — SiH2—
stretching frequencies toward higher values, as was found for difluorosilane
and monochlorosilane.
254 Chapter 15: Organosilicon Compounds

15-2.2. The - S i H 2 - Deformations

For compounds with the R—SiH2—R type of hnkage, the vibrational
frequencies of the — SiH2— scissoring m o d e , the — SiH2— wagging m o d e ,
the — SiH2— twisting m o d e , and the — SiH2— rocking m o d e were reported
to be located in the regions of 950-930 c m " \ 900-840 c m " \ 690-560 c m " \
and 540-480 c m ~ \ respectively (4). Halogenation on the Si a t o m appears
to shift the above correlated frequency regions upwards somewhat, as
demonstrated in Table 15-2.

15-3.
THE S i - H GROUP
15-3.1. The Si - H Stretching Mode
The Si —H stretching frequencies are sensitive to the inductive effect of the
substituents. The frequency increases as the sum of the electronegativities of
the substituents increases [13]. The characteristic frequencies of the Si—H
compounds are hsted in Table 15-3, In IR spectra, the S i - H stretching

Table 15-3.
The Group Frequencies of SiH Vibrations (cm"^)

Compounds Si-H Stretch IR R Si-H Bending IR R Reference

H-SiR3 2110-2094 842-800 s 1,3b, 11

H-SiR2Ar 2115-2103 842-800 s l , 3 d , 11
H-SiRAr2 2125-2115 842-800 s l , 3 d , 11
H-SiAr3 2132-2112 vs m'' 842-800 s 1,3c, 11
H-SiMe2Cl 2171 s 842* s 3e
H-SiMeCl2 2215 s 837* s 3e
H-SiF3 2282 1
H-SiBr3 2236 1
H-Si(OMe)3 2203 1
H-Si(OEt)3 2194 s 880/860* s 3f
H-SiMe20SiMe2 2129 s 834* m 3g
-(SiHMe-0)„- 2166 s 838* s 3h
-(SiHPh-O),- 2180 s 19
l-Hydrosilatrane 2088 s vs 935 vs sh 12, 16,17
(H-Si(OCH2CH2)3N)

"The relative Raman intensity is shghtly lower than that of the 1590cm"^ band of the
aromatic stretching mode.
* Tentative assignment.
15-4. The S i - C Stretching 255

m o d e appears in the region of 2110-2089 cm"^ for trialkylsilanes

[1, 3b, 11, 25]. The substitution of the alkyl groups on the Si atom by aryl
groups tends to increase the Si—H stretching frequencies, and a region of
2132-2112 cm~^ [1, 25] was reported for triarylsilanes. The Si—H stretch-
ing frequencies of some monoaryl- and diarylsilanes are intermediate [25].
Lee Smith [13, 15] and T h o m p s o n [14] b o t h have reported formulas that
ahow the prediction of the Si—H frequencies from the parameters that are
characteristic of the substituents on the Si a t o m . The (XYZ)SiH frequency
in dilute CCI4 solution can be calculated by a summation of wavenumber
components, one for each of the three substituents. A selection of these
components is given as follows in cm"^ [13], if there are no Si—O—Si
groups: F 760.8, Cl 752.8, Br 745.3, O M e 734.4, OEt 732.0, H 724.8,
P h 708.7, Me 705.9, Et 699.1. For example, (F3)SiH stretch is calculated as
3 X 760.8 = 2282.4 cm"^ (observed 2282 cm"^). The SiH frequencies in
siloxanes are calculated by a slightly m o r e complex function [13].
As illustrated in Table 15-3, halogenation and the presence of an alkoxy
group wih also, although to a lesser extent, increase the Si—H frequency. In
some cases, the electronic structure of the Si atom can be probed by the
Si—H frequency [16]. The exceptionally low Si—H stretching frequency of
1-hydrosilatrane in comparison with other alkoxy-substituted Si—H com-
pounds has been attributed to the formation of an intramolecular b o n d
between the Ν a t o m and the Si a t o m in the cychc structure of the molecule
[12,16,17].

15-3.2. The S i - H Deformation

The Si—Η bending occurs in a lower region, 842-800 c m ~ \ for alkyl and
aryl silanes [11] with strong IR intensity [3b-3d]. A strong IR band is found
in the spectra of chlorinated silanes [3e], 1,1,3,3,-tetramethyldisiloxane
[3g], and polymethylhydrosiloxane [3h] near the higher-frequency end of
the above region (see Table 15-3). In Table 15-3, note the extraordinarily
high value of the Si—Η bending frequency of 1-hydosilatrane at 935 c m ~ ^
which is about 100 cm"^ higher than the suggested region of 842-800 c m " \
due to the unusual N ^ S i b o n d of the molecule [12, 16, 17].

15-4.
THE S l - C STRETCHING
The Si—C stretching frequencies are reported in the range of 900-500 c m " '
[1]. Based on the available data, it appears that the R a m a n intensity of the
256 Chapter 15: Organosilicon Compounds

Table 15-4.
The S i - C Stretching Frequencies (cm"^)

Compounds Frequency (cm) IR R Reference

Si(CH3)4 860 1
-Si(CH3)3 sym. str. 715-680 1
antisy. str. 660-485 1
Me-Si-Me 730-650 1
—O—SiMe (end group) 850-840 1
(side chain) 800-770 1
R-SiH3 Pc 750-740 20
PH 690-685 20
R - S i - R ' (R,R' = Me, Et; Et, Et; or Me, Pr):
Si(H2)-CH3 str. 730-710 m-s s-vs 10
Si(H2)-C(H2) str. 760-610 10
Pc above 700 m-s m-vs
PH below 700 mw-w vvs
CH2=CH-SiH3 624 m m 21
HjC-Si-Si-CHj 4
—(Si—0)„—, siloxanes near 800'' 19

'See text for further discussion.

Si—C stretching m o d e is very distinct, while the IR intensity can vary from
weak to strong.
The Si—C stretchings are found to have considerable vibrational eouphng
with other vibrations of the neighboring moieties [10], and the frequencies
are very dependent on the nature of the substituents [1]. T h e typical Si—C
frequencies are summarized in Table 15-4. The eouphng of the S i - C
stretehing vibration with other neighboring vibrations can be illustrated by
the 800 cm"^ IR band of the open-chain dimethyl siloxanes. This IR band
of dimethyl siloxane was assigned by H u m m e l [19] to the C—Si—C
stretching m o d e , b u t Smith [15] assigned it t o the methyl rocking m o d e .
Colthup et aL [11] pointed out that there is probably vibrational coupling
between the Si—C stretching mode and the CH3 rocking m o d e for the
Si—CH3 group.
Like those of dialkylsulfide, the rotational conformations of dialkyl-
silanes m a y be classified as Pc and PH conformations. M o r e t h a n one b a n d
in the vibrational spectra of dialkylsilanes can be attributed to the S i - C
stretching modes due to the rotational isomers. The C—Si stretching
frequencies of dialkylsilanes are found to be correlated with the rotational
conformations. Matsuura and coworkers [10] have correlated the S i - C
stretching frequencies of dialkylsilanes, based on a normal coordinate
analysis of three dialkylsilanes, t o be above 700 cm"^ for the Pc isomers.
15.5. Si—C Groups 257

and below 700 cm"^ for the PH conformers. The IR intensities appear to be
medium-to-weak, and the R a m a n intensities are from medium-strong to
strong.
For monoalkylsilanes, the Si—C stretching frequencies of the Pc con-
formation are reported to be in the region of 750-740 c m " \ while those of
the PH conformation are found in the region of 690-685 cm"^ [20].
The SiCC bending of vinylsilane is located at 284 cm"^ with weak R a m a n
intensity [21].

15-5.
S i - C GROUPS

15-5.1. Si-R

The CH3 in the Si—CH3 group has a very strong, sharp IR b a n d at

1280-1255 cm"^ (symmetric deformation) and a weak b a n d near 1410 cm"^
(antisymmetric deformation). The SiCH3 rock (plus probably some S i - C
stretch interaction) has IR bands at 870-750 cm"^ [24]. See Table 15-5.
The S i - C 2 H 5 group has IR bands at 1250-1220, 1020-1000, and 970-945
c m " ^ The group Si—CH2—R has a weak b a n d near 1410 cm"^ (CH2 defor-
mation), and a medium-intensity IR b a n d at 1250-1200 cm"^ (CH2 wag) [24].

Table 15-5.
S i - C Groups [24]

Assignment

SiCHj ca. 1410 I R : w CH3 antisym. str.

1280-1255 I R : s CH3 sym. str.
870-750 IR : s involves CH3 rock
Si-CHj-R ca. 1410 I R : w CH2 def.
1250-1200 I R : m CH2 wag
Si-CH=CH2 1615-1590 I R : m C = C str.
1410-1390 I R : m =CH2 def.
1020-1000 I R : m = C H wag
980-950 I R : m =CH2 wag

Si-phenyl ca. 1430 IR : m ring str.

1125-1100 I R : s ring + Si—C str.
ca. 730 IR : m ring CH wag
ca. 700 IR : m ring bend
258 Chapter 1 5: Organosilicon Compounds

15-2.2. Si-CH=CH2
The S i - C H = C H 2 siUcon-vinyl group has IR bands at 1 6 1 5 - 1 5 9 0 c m " '
( C = C stretch), 1 4 1 0 - 1 3 9 0 c m " ' (CH2 deformation), 1020-1000 ( = C H
wag), and 980-950 c m " ' ( ^ C H j wag) [24].

15-5.3. Sl-Phenyl
When a siUcon atom is directly attached to a phenyl g r o u p , a substituent-
senstitive ring m o d e , which involves some Si—C stretch, is seen in the IR at
1 1 2 5 - 1 1 0 0 c m " ' . Other phenyl IR bands are seen near 1430, 730, and
700 c m - ' [24].

15-6.
THE S i - O STRETCHING
The IR freqencies of some organosihcon c o m p o u n d s containing the Si—Ο
hnkages are hsted in Table 15-6.
Smith [15] has studied the correlation between the Si—Ο vibrational
frequencies and the inductive effects of the substituents on the sihcon a t o m .
In general, a higher Si—Ο stretching frequency is observed for compounds
with substituents of higher electronegativity on the sihcon atom [15, 16].
The Si—O—C stretching frequencies of alkoxysilanes (Si—OR) are
located in the region of 1100-1000 c m " ^
The Si—O—Si stretching frequencies of siloxanes are characterized by
the very strong IR complex in the region of 1100-1000 cm~^ [1, 19]. Long-
chain siloxanes have two broad IR bands near 1090 and 1020 c m " ^ The
possible spectral interference for the assignment of these vibrational modes
is the Si—O—S stretching mode of alkoxysilanes.
The Si—O —Si stretching frequencies of cyclic siloxanes are correlated
with the ring size [15,23]. The Si—O —Si stretching frequencies of the
( S i — 0 ) 3 cyclotrisiloxanes are located in the region of 1020-1010 c m " \
while the cyclotetrasiloxanes have bands near 1080 c m " \ The Si—O —Si
stretching frequency of a cyclopentasiloxane, which is located near 1100
c m ~ \ is the highest frequency found for cyclosiloxanes. A gradual decrease
of the Si—O—Si stretching mode from llOOcm"^ was reported for cyclo-
siloxanes larger than pentamers. For cyclodecasiloxanes, the Si—O —Si
stretching frequency is near 1050 c m " ^
The S i — O - H group has a strong IR band involving Si—Ο stretch at
920-830 c m " ' [24]. The O H stretch b a n d is hke that in alcohols, 3700-3200
cm~\ for free or hydrogen-bonded O H [24].
15.8. Si-Halogen 259

Table 15-6.
The Si—Ο Stretching Frequencies (cm~^)

Reference

Alkoxysilanes:
Si-OCH3 1110-1107
1100-947
Si-OEt 1100-1075 1, 15
1060-1040
970-940
Si-0(/-Pr) 1060-1025 15
Si-OH 920-830 15
S i - Ο Ac 955-935 15
Si-OPh 970-920 15
Siloxanes:
Si-O-Si 1100-1000 1, 19
Open-chain siloxanes 1093-1076 1
1055-1024
Cyclotrisiloxanes 1020-1010 1, 15
Other cyclosiloxanes 1100-1050 1, 15
Cyclic aromatic siloxanes:
(SiPh20)3 1015
(SiPh20)4 1100

15-7.
THE Si-Si STRETCHING
D u r i g a n d C h u r c h [5] h a v e r e p o r t e d t h a t t h e S i — S i s t r e t c h i n g m o d e o f
d i s i l a n e ( H 3 S i — S i H 3 ) gives rise t o a s t r o n g R a m a n b a n d a t 423 c m " ^
S i m i l a r r e s u l t s w e r e r e p o r t e d b y O h n o et al, [4] f o r d i m e t h y l d i s i l a n e
( C H 3 S i H 2 — S i H 2 —CH3). T h e s e a u t h o r s f o u n d t h a t d i m e t h y l d i s i l a n e s give
rise t o t w o s t r o n g a n d p o l a r i z e d R a m a n b a n d s a t 424 a n d 413 c m " ^ t h a t c a n
be attributed t o t h e Si—Si stretching m o d e .

15-8.
Si-HALOGEN
The Si—CI g r o u p absorbs in the IR at 6 2 5 - 4 2 0 c m " ' , with subregions for
SiClj at 6 2 0 - 5 7 0 c m " ' I R : s a n d 5 3 5 - 4 5 0 c m " ' I R : m , for SiClz at 6 0 0 -
535 c m " ' IR : s and 540-460 c m " ' IR : m , a n d for SiCl at 550-470 c m " ' [24].
See Table 15-7.
260 Chapter 1 5 : Organosilicon Compounds

Table 15-7.
Si-Halogen [24]

SiF3 980-945 IR : s
910-860 I R : m
SiF2 945-915 I R : s
910-870 I R : m
SiF 920-820 IR : m
SiCl3 620-570 IR : s
535-450 IR : m
SiCl2 600-535 IR : s
540-460 IR : m
SiCl 550-470 IR : m

T h e SiF g r o u p absorbs in the IR at 1000-800 cm with subregions for

SiFj at 980-945 cm-^ I R : s a n d 910-860 c m ' ^ I R : m , for SiFz at 945-915
c m - ' I R : s a n d 9 1 0 - 8 7 0 c m " ' I R : m , a n d for SiF at 9 2 0 - 8 2 0 c m - ' [24].
Halosilanes react readily with moisture t o form siloxanes [24].

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