CHAPTER 13

Cumulated Double Bonds

13-1.

INTRODUCTION
Examples of cumulated double bonds are alines
(/C=C=C\)
ketenes ( / C = C = 0 ) , ketene imines ( / C = C = N ) , diazo compounds
( > C = N = N ) , isocyanates ( N = C = 0 ) , isothiocyanates ( N = C = S ) ,
isoselenocyanates ( N = C = S e ) , azides ( N = N = N ) , and carbodiimides
( N = C = N ) . In these X = Y = Z types of groups, the vibrations of the
two double bonds are strongly coupled and result in out-of-phase and inphase stretchings. Colthup et aL [1] noted that the out-of-phase stretch
band of the group X = Y = Z is located in a region near that of the tripleb o n d stretching, and the in-phase stretching occurs in a region close to that
of the single-bond stretchings. This statement is fully supported by the
characteristic frequencies hsted in Table 13-1 for various X = Y = Z types of
compounds.
Since the in-phase m o d e exhibits stretching frequencies very similar to that
of the single b o n d , couphng between the in-phase X = Y = X stretching and
stretching vibrations of the neighboring single bonds is expected. As a
result, the in-phase stretching is more sensitive to the substituents on the
X = Y = Z group than the out-of-phase stretching m o d e . One may assume
that the out-of-phase stretch of X = Y = Z should exhibit strong infrared
absorption and weak R a m a n intensity, and vice versa. While this is largely
true for most cumulated double b o n d s , many ketenes and diazo compounds
213

214

Chapter 1 3 :

Cumulated Double Bonds

Table 13-1.
The Characteristic X = Y = Z Stretching Frequencies

Compounds
>C = C - C H 2

>c=c==o
>C=C=N>C=N=N
>N=C=0
>N-=C = S
-N=N=N
-N=C=N-

X=Y=Z
Out-of-Phase
Stretch

IR

1980-1901
2197-2085
2060-2000
2113-2013
2300-2250
2200-2000
2169-2080
2152-2128

vs
vs
s
vs
vs, br
vs, br
vs
vs

vw
var.
m-mw,
vw-O
m-mw,
ms-m,
w

X=Y = Z
In-Phase
Stretch
1095-1076
1420-1120
-1233
1389-1333
1450-1400
1090-925
1343-1177
-1460

IR

vw
vs
s
vs
w

vs,
s,
s,
vs-m,
s,
s,
s,
s,

w
w

appear to have strong IR and R a m a n bands in both regions. Splitting of the

out-of-phase stretching band due to the rotational isomers [16, 17] and the
Fermi resonance effect [39, 63, 65] were observed in some cases.

13-2.
ALLENES(>C=C=C<)
The most characteristic frequencies of alines arise from the out-of-phase
and in-phase C = C = = C stretchings. These vibrations are found in the
regions of 2000-1900 cm"^ and 1130-1060 c m " \ respectively [1].
Table 13-2 illustrates the stretching frequencies of selected alines. A
good review of the out-of-phase C = C = C stretching frequencies of 58
substituted ahenes can be found in reference 4. Generally, both stretching
frequencies are lowered by halogenation and conjugation (see Table 13-2).
For R 2 P ( 0 ) - H C = C = C H 2
and X C ( = 0 ) - H C = C = C H 2
types of
alines, an IR doublet was reported in the region for out-of-phase
/ C = C = C H 2 stretching [16, 17]. This p h e n o m e n o n is attributed to the
effect of rotational isomerism [17]. The symmetrical c o m p o u n d tetramethyl
aline, ( C H 3 ) 2 C = C = C ( C H 3 ) 2 , has only weak IR absorption in the 20001900 cm"^ region.
The assignment of the in-phase C = C = C stretching m o d e is controversial. A previous study by Piaux and G a u d e m a r [11] designated the two
strong-to-medium R a m a n bands at about 1130 cm"^ and UOOcm"^ as the
in-phase C = C = C stretching m o d e of m o n o Ai-alkyl alines. M o r e recently.

13-3.

Ketenes ( > C = C = 0 )

215
Table 13-2.

The C==C=C Stretching Frequencies (cm~^) of Alines

Compounds
H2C=C=CH2
H2C==C=HR
RHC=C=CHR
H2C=C=CR2
H 2 C = C = C H X (X = CI, Br, I)

H2C = C=CHC6H5
(Me)(CR20H)C=C = C H - 0 ( C = 0 ) N R 2
-CH=C = CH-(Me)C=CHCH = C ( M e ) - C H = C = C H - ( M e ) C = C H H2C=C=CR(C=0)R
H 2 C = C = C H ( C = 0 ) Y (Y: O H , NH2, OR)
(Et)(Ph)C=C=CH (C=O) R2P(0)HC=C=C(Me)R

C=C=C
Out-of-Phase
Stretch
1957
1980-1945
1955-1930
1930-1915
1963-1953
1925
1980-1970 (IR)
1927 (IR)
1901 (IR)
1945-1940 (IR)
1930-1910 (IR)
-1930
1960-1949 (IR)

IR

s
ms
ms
ms
m
s

vs-w

c = c = c
In-Phase
Stretch

IR

1076
vs,
-1080
vw
s
-1080
vw
s
vw
-1080
s
1095-1076
vs, p
1080,1060

Ref.
2-5
4, 13, 14, 36
4, 36
4, 36
4, 6 , 7
4,10-12,36
8
9
9
15
16
15
17

investigation indicated that the C = = C = C in-phase stretching occurs at

1095-1060 cm"^ for most alines (see Table 13-2). In the case of
C H 3 C H = C = C H 2 , the prominent R a m a n bands at 1132 cm~^ ( R : v s , p)
and 1102 cm"^ ( R : m , dp) are assigned to CH3 and CH2 wagging modes,
respectively [14]. The in-phase C = C = = C stretchings of phenyl ahenes are
expected to occur at 1080 cm~^ and 1065 c m " ^
The spectra of alines are further characterized by the allenic CH vibrations, which fah in the regions near those of ethylenic CH vibrations. For
aline (H2C=C=CH2) itself, the CH stretchings, CH2 scissoring, and
=CH2 wagging are at 3067 cm"^ and 2996 cm~\ 1440 c m " \ and 848 c m " ^
respectively [2-5]. The CH vibrations of substituted alines are situated at
very similar regions as those of ahene [3, 4, 6, 14]. The overtone of =CH2
wagging near 1700 cm~^ is also observed in the infrared spectra.
The C = C = C bending of aline occurs strongly at 356 cm"^ in the
R a m a n spectrum [3]. However, much higher frequencies (625-592 c m " ^
and 548-485 cm"^) were reported for the haloahenes [6].

13-3.
KETENES ( > C = C = 0 )
The two C = C = 0 stretchings are located at a higher frequency region than
those of ahenes (see Table 13-1 and Table 13-3). Although the out-of-phase
C = C = 0 stretching occurs in the same regions as the C = C stretching of

216

Chapter 13:

Cumulated Double Bonds

Table 13-3.
The C = C = 0 Stretching Frequencies (cm"^) of Ketenes
c = c = o

Compounds
H2C=C=0
Me2C=C=0

(CF3)2C=C=0
(C6H5)2C=C=0
(Me3Si)HC=C=0
(Et3Si)HC=C=0
(Cl3Si)HC=C=0
(Me3Si)2C=C=0

c = c = o

Out-of-Phase
Stretch

IR

2153
2122
2197
2105
2112
2115
2165
2085

vs
vs
vs
vs
vs
vs
vs
vs

R
a

m,

In-Phase
Stretch

IR

Ref.

1130
1374
1420
1120
1270
1275
1296
1295

s
s
s
w
vs
s
m
m

s,p

ms

18, 19, 24,25

20
21,22
22
23
23
23
23

): Intensity not available.

monosubstituted acetylenes (2130-2100 cm"^), these two absorptions can

usually be differentiated by the infrared intensity. The C = C = 0 stretchings
can be further differentiated from C = C stretching by the presence of a
medium-to-strong IR b a n d originating from the ketene in-phase stretching
at the region of 1420-1120 c m " ^
Although the R a m a n intensities of these two C = C = 0 stretching modes
are medium to strong in many cases, they are not necessarily the strongest
bands in the R a m a n spectra. In the case of ( C F 3 ) 2 C = C = 0 , the strongest
R a m a n b a n d was found at 766 c m " \ which is attributed to symmetric
C2C stretching of the (CF3)2C= moiety.
Ketenes' stretching frequency and intensity are sensitive to substitution.
For example, the characteristic C = C = 0 stretchings of H 2 C = C = 0 occur
at 2153 cm~^ (IR : vs; R : w) and 1130 cm~^ (IR : s; R : vs) for out-of-phase
and in-phase modes, respectively [ 1 8 , 1 9 , 2 4 ] . O n methylation, the outof-phase and in-phase C = C = 0 stretching bands of (CH3)2 C = C = 0
shift t o 2134cm"^ ( I R : v s ) and 1374cm"^ ( I R : v s ) , respectively [20].
Further fluorination on the methyl groups of the methylated ketene
increases the out-of-phase and in-phase C = C = 0 stretchings to 2179 cm~^
( I R : v s ; R : m , p) and 1429 cm"^ ( I R : s , R : s , p), respectively [21,22].
However, conjugation of a phenyl group to the C = C = 0 moiety lowers
the stretching frequencies. ( C 6 H 5 ) 2 C = C = 0 is a good example, which
exhibits a very strong IR band at 2105 cm"^ (out-of-phase) and a weak IR
b a n d at 1120cm"^ (in-phase) [22]. In addition, the attachment of a R3Sigroup to the C = C = 0 moiety reduces the C = C = 0 stretching frequencies
(see Table 13-3). However, the stretching frequencies of silylketones can

13-4.

217

Ketene Imines ( > C = C = N - )

be inereased by chlorination. For example, the out-of-phase C = C = 0

stretehing of C l g S i H C = C = 0 occurs at 2165 cm"^ (gas; IR : vs), and the
in-phase m o d e at 1296 cm"^ (gas; I R : m ) [23].
T h e C = C = 0 bending frequencies are expected t o occur in the spectral
regions close to those of C = C = C bendings. The C = C = 0 bendings of
( C H 3 ) 2 C = C = 0 and ( C F 3 ) 2 C = C = 0 are assigned to the IR bands in the
regions of 676-668 cm"^ (IR : m-w) and 541-486 cm"^ (IR : ms).

13-4.
KETENE IMINES ( > C = C = N - )
The C = C = N stretching frequencies of ketene imines are summarized in
Table 13-4. Stevens and French [27] observed a characteristic IR b a n d for
Y 2 C = C = N - Y (where Y is alkyl or aryl) in the region of 2050-2000 c m " S
which was assigned t o the out-of-phase C = C = N stretching m o d e . For Nmethyl ketene imine, out-of-phase stretching occurs at a somewhat higher
value (2060 cm"^), and in-phase C = C = N stretching exhibits a medium IR
band at 1233 c m " ^
Table 13-4.
Characteristic Stretching Frequencies (cm"^) of Ketene Imines ()>C=C=N)
and Diazo Compounds ( > C = N = N )

Compounds

X=Y=Z
Out-of-Phase
Stretch

A . Ketene Imines
H2C=C=N-CH3
Y 2 C = C = N - Y (Y: - R or - A r )
(Me-S02)2C=C=N-Me

2060
2050-2000 (IR)
2170 (IR)

B. Diazo C o m p o u n d s
H2C=N=N
RHC=N=N
R2C=N=N
R(C=0)-CH=N=N
Ar(C=0)CH=N=N
R(C=0)-CR=N=N
HC=C-CH=N=N
(CN)2C=N=N
(CF3)2C=N=N

2102
2049-2036
2032-2012
2100-2087
2133-2106
2076-2057
2060
2147
2136

): Intensity not available.

*R = CH3.

IR

X=Y=Z
In-Phase
Stretch

IR

Ref.

1233

26
27
1

vs
vs
vs
vs

vs
vs
vs
vs

(m,p)

(mw, p)
s

1170
1389-1333
1389-1333
1337*
1353-1351
1304*
1168
1246
1378

s
s
vs
vs

s
vs
s
vs

m,

vs,

w,p

28,29
30
30
30, 33
30,31
30, 32
34
35
21

Chapter 13:

218

Cumulated Double Bonds

13-5.
DIAZO COMPOUNDS ( > C = N = N )
The out-of-phase and in-phase C = N = N stretchings of diazo compounds
fah in regions similar to those of C = C = 0 stretchings (see Table 13-1
and Table 13-4). For diazomethane (H2C==N=N), the stretchings are at
2102 cm"^ and 1 1 7 0 c m ~ ^ These stretching frequencies are susceptible to
substitution. In the case of (CF3)2C=N=N, the presence of the fluorine
atoms near the C = N = N moiety shifts the out-of-phase and in-phase
C=N==^N stretchings to the higher frequencies of 2136 and 1 3 8 0 c m ~ ^
respectively [21]. Interestingly, the conjugation of the C = N = N grouping
with other unsaturated moieties such as carbonyl and aromatic groups
increases the out-of-phase C = N = N stretching frequency to a region higher
than that of alkyl diazocompounds. For diazocarbonyl c o m p o u n d s , this
unusual frequency enhancement is rationalized by the increasing triplebond character due to the contribution of the resonance form (II), as in the
equation
0 = C - C H = N = N

(I)

-C=CH-N^N.
(II)

The significance of resonance form (II) is also demonstrated by the lowering

of the C = 0 stretching frequency to 1647-1605 cm"^ for diazo ketones.
A similar effect is observed for quinone diazines [73, 74].

13-6.
ISOCYANATES ( - N = C = 0 )
There are only a limited number of studies on the vibrational analysis of this
class of c o m p o u n d s . Table 13-1 compares the characteristic N = C = 0
stretching frequencies of isocyanates with other X = Y = Z moieties.
Generally, the out-of-phase N = C = 0 stretching mode absorbs infrared
strongly in the region of 2300-2250 c m " \ while the R a m a n intensity of this
vibrational m o d e is usually weak or undetectable [37-40, 47].
Stretching frequencies of N = C = 0 are generally not very sensitive to
substitution. For example, conjugation with a phenyl group varies the outof-phase stretching frequency by only a smah a m o u n t . For aryl isocyanates,
this frequency is in the region of 2282-2267 c m " ^ (IR : strong and broad
band) [41]. Attachment of the N = C = 0 moiety to a heavy atom (e.g.. Si,
Ge, or S) results in little variation of the N = C = 0 stretching frequency
from those of alkyl isocyanates [38, 42-46].

13-7,

Isothiocyanates ( - N = C - S )

219

The IR band of the N = C = = 0 out-of-phase stretching m o d e can be

differentiated from the C = N stretching band (2270-2210 cm"^) by its very
intense and broad features. This absorption is often accompanied by
shoulders on both sides of the IR b a n d , and it is best illustrated by the IR
spectra of aryl isocyanates [41,47]. In the case of allyl isocyanate, such
complex band structures were interpreted as various combination bands
enhanced by Fermi resonance with the out-of-phase N = C = 0 stretch m o d e
in the region near 2200 c m " ^ [39].
The in-phase N = C = 0 stretching is assigned to a polarized strong
R a m a n band in the 1450-1400 cm~^ region for methyl, ethyl, and isopropyl
isocyanates [37-40]. Although the R a m a n spectrum of tertiary butyl isocyanate has been reported [42], the assignment of the in-phase N = C = 0
stretching m o d e is not certain. Nevertheless, a strong, polarized band
observed at 1402 cm"^ is assigned to the in-phase N = C = 0 m o d e . The
presence of a heavy a t o m adjacent to the N = C = 0 group caused a wider
spectral region (1478-1357 cm"^) for this vibration [38,42-46]. The
infrared intensity of the N = C = 0 in-phase stretch is weak in the majority
of cases. However, the IR absorption in this region becomes strong to
medium when two N = C = 0 groups attach to the same a t o m or adjacent
atoms as a result of out-of-phase interaction between the two in-phase
N = C = 0 stretchings [38, 43, 48].
The assignment of in-phase N = C = 0 stretching for phenyl isocyanate is
controversial. H a m and Wilhs [50] attributed a strong IR band at 1108 cm"^
to this vibrational m o d e , while Stephenson et al. [49] assigned the polarized
strong R a m a n band at 1443 cm"^ to the same motion. Furthermore, a
polarized strong R a m a n band, which is not observed in the R a m a n spectra
of other types of substituted benzene, is notable in the region of 15401500 cm"^ [47] for most ortho-substituted phenyl isocyanates. This polarized
strong R a m a n band is hkely to involve the in-phase N = C = 0 vibration.
The N = C = 0 bending modes exhibit a poorly defined band in the
650-600 cm"^ region for the hquid-state IR spectra of alkyl isocyanates,
and a prominent band at 600-590 c m " ^ for the sohd-state IR spectra [37].
For the allyl isocyanate, the N = C = 0 bending is not observed in the IR
spectra but shows up as a weak R a m a n scattering at 572 c m " ^ [39].

13-7.
ISOTHIOCYANATES ( - N = C = S )
The out-of-phase N = C = S stretching of isothiocyanates gives rise to a very
strong and b r o a d IR absorption in the region of 2200-2000 c m " \ which

220

Chapter 1 3 :

Cumulated Double Bonds

is approximately 100 cm"^ below the IR absorption of isocyanate groups.

Similar to the IR spectra of organic isocyanates, the out-of-phase N = C = S
stretching features a multiband structure. For alkyl isothiocyanates, a very
strong band at 2150-2050 cm"^ with a medium shoulder at 2221-2150 cm"^
is the characteristic IR pattern [39, 50-54, 56, 57]. The multiple absorptions
of aromatic isothiocyanates shift to the 2135-2015 cm"^ region [49, 50, 55].
The absorption complexity in this region was attributed to Fermi resonance
of combination tones with the N = C = S out-of-phase stretching mode [39].
Interestingly, the R a m a n intensities of the N = C = S out-of-phase stretching
modes are prominent and polarized in many cases [39, 49-51].
The out-of-phase and in-phase stretching frequencies are little affected
by the attachment of a heavy atom such as Si or Ge. Several studies on
silyhsothiocyanates [38, 58, 59, 61] and germyhsothiocyanate [60, 62]
indicate that their characteristic N = C = S stretchings occur in regions near
those of alkyl isothiocyanates. However, interaction between N = C = S
groups should be considered when more than one N C S group is present on
the same atom.
The in-phase N = C = S stretching m o d e of alkyl isothiocyanates was
assigned to a polarized strong R a m a n band in the region of 690-650 c m " ^
[50]. However, most authors preferred the polarized, strong R a m a n band
at 1090-980cm"^ for this vibrational m o d e [39, 5 1 , 52, 56]. Recently, the
normal coordinate analysis of methyl and ethyl isothiocyanates by Durig
et aL [51, 52] revealed extensive mixing of N = C = S stretching and C
stretching. Such vibrational couphng results in two strong polarized R a m a n
bands in the 1090-1035 cm"^ and 690-650 cm"^ regions. For aromatic
isothiocyanates, the in-phase stretching occurs in a lower frequency region,
936-925 c m " \ with strong-to-medium IR absorption but weak R a m a n
intensity [49, 50, 55].

13-8.
ISOSELENOCYANATES ( - N - C - S e )
The infrared spectra of alkyl isoselenocyanates have been studied by
Franklin and coworkers [53]. The out-of-phase and in-phase N = C = S e
stretching modes of methyl isoselenocyanate ( C H 3 C H = C = S e ) occur at
2182 cm"^ and 983 cm~\ respectively.
In the case of higher homologues, the out-of-phase stretching m o d e fahs
in the region of 2142-2100 c m " ^ while the in-phase stretching is displaced
to a much lower region (559-504 cm"^). In addition, rotational isomerism
may produce a doublet for the N = C = S e stretching absorptions.

13-10.

Carbodiimides ( - N = C = N - )

221

13-9.

AZIDES ( - N = N = N )
Lieber et al. (63-65) studied the group frequencies of organic azides such as
alkyl azides (RN3), aryl azides (ArN3), acid azides ( C ( = 0 ) N 3 ) ,
carbamyl azides ( > N C ( = 0 ) - N 3 ) , vinyl azides (H2C=CRN3), and aazido ethers (RXCH2N3, X: O, S, or N) by infrared spectroscopy.
Generally, the out-of-phase N = N = N stretchings faU in the region of 21692080 cm"^ ( I R : v s ) , and the corresponding in-phase m o d e occurs in the
region of 1343-1177 cm"^ (IR : w). Other bands with weaker IR intensities
near 2400 and 2200 cm"^ are observed when an unsaturated moiety (e.g.,
A r , C = C , or C = 0 ) is adjacent to the N3 group or when a heteroatom
(O, S, or N) is attached to the carbon a t o m at the a position of the N3
group. This splitting of the N = N = N out-of-phase bands is attributed to
Fermi resonance of the N = N = N out-of-phase stretching with the combination tones of N = N = N in-phase and C stretchings, and other
low-lying frequencies. Similar results were reported recently for 2-azido1,3-butadiene [66, 68], 2,3-diazido-l,3-butadiene [67, 68], and 2,6-diphenyl
azide [69].
The out-of-phase N = N = N stretching m o d e exhibits medium-to-strong
R a m a n intensity, while the in-phase m o d e displays strong R a m a n intensity.
Examples are methyl azides (R: 2104 c m " ^ ms, 1 2 7 6 c m " S vs) [12] and
2-azido-l,3-butadiene (R: 2111 c m " \ m, p , 1 2 2 4 c m " \ s, p) [66].

13-10.

CARBODIIMIDES ( - N = C = N - )
The infrared spectra of R N = C = N R types of compounds has been
explored by K h o r a n a [70,71] and by Meakins and Moss [72]. A review
on the infrared and R a m a n spectra of carbodiimides was given by Mogul
[75]. Generally, the N = C = N out-of-phase stretching of alkyl and aryl
carbodiimides absorbs infrared strongly in the 2152-2128 cm"^ region. The
IR intensity of this band is about 2.5 times as strong as the normal ketonic
carbonyl absorption. The in-phase N = C = N stretching m o d e occurs near
1460 cm"^ with strong R a m a n scattering effect. Attachment of a Si atom to
the N = C = N moiety shifts both frequencies toward the higher value. For
silyl carbodiimides, the out-of-phase and in-phase stretchings are located at
2260-2180cm"^ and near 1 5 0 0 c m " \ respectively [76,77]. For germyl
carbodiimide, N C N bands are at 2168-2140 cm"^ and 1419cm~^ [78].

Chapter 13:

222

Cumulated Double Bonds

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