Spectrochimica Acta, Vol. 45A, No. 9, pp. 905-909, 1989. 0584-8539/89 $3.00+0.

00
Printed in Great Britain. 1989 Pergamon Pregs pie

An infrared study of the nitro-nitrito linkage isomerization in solid

nitro- and nitritopentamminecobalt(lll) chloride
A. M. HEYNS and D. DE WAAL
Department of Chemistry, University of Pretoria, 0002 Pretoria, South Africa

(Received 21 February 1989; accepted 1 March 1989)

Abstract--The photochemical isomerization reaction of [Co(NH3)sNO2]CI 2 to [-Co(NHa)sONO]CI 2 has

been studied in the solid state by means of i.r. spectroscopy. The reaction is first order with k = 2.53 _+0.05
x 10-4s -1 and is much faster (tl/2 =49min) than the well-known spontaneous nitrito --, nitro iso-
merization (tl/2 ----6 days). The i.r. bands of both the NH 3 and ONO--groups in the range 4000-50 cm- 1
indicate minor differences between the structures of freshly and photochemically prepared
[Co(NH3)sONO]CI 2. The far i.r. spectra indicate the disorder existing in the intermediate products during
the isomerization processes.

INTRODUCTION EXPERIMENTAL

When the ambidentate N O 2 ligand is coordinated to a
metal ion, e.g. the cobalt (III) ion, it is well-known that
either the nitro or nitrito complexes can be formed.
[Co(NH3)sNO2]CI2 is thermodynamically more
stable than I-Co(NH3)sONO]CI 2, but the nitrito com-
plex can nevertheless be synthesized [1, 2]. The con-
version of the red [Co(NH3)sONO]CI2 to the yellow
[Co(NH3)sNO2]CI2 has been extensively reported in
the literature [3-7] and i.r. spectroscopy has been one
of the important tools used in studying the rate of
isomerization of the unstable nitrito to the more stable
nitro complex [5,7].
GRENTHE and NORDIN [8] investigated the nitrito
to nitro isomerization of [ C o ( N H 3 ) 5 O N O ] C I 2 by
means of crystallographic methods and concluded
that the [Co(NH3)sNO2]CI 2 so obtained is an unsta-
ble intermediate which very slowly converts to a stable
nitro product with the same formula but with a
different crystal structure from that of the intermediate
nitro product. The intermediate and final products
have space groups of P21nb [8] and C2/c [9] respect-
ively. The final product, except for a slight disorder,
has the same structure as freshly prepared
[ C o ( N H 3 ) s N O 2 ] C I 2 [8].
O n the other hand, it was also reported that the
nitro --, nitrito photoisomerization gives rise to a
nitrite c o m p o u n d with a structure different from that
of freshly synthesized [ C o ( N H 3 ) s O N O ] C I 2 [8]. This
photoreaction could be intramolecular and probably
proceeds via a seven-coordinated transition state [8].
In view of the above findings, we have undertaken
an i.r. study of the rate of the nitro --, nitrite photo-
isomerization which has, to the best of our knowledge,
not been reported before. Furthermore, we have
recorded the full i.r. spectra down to 50 cm -1 of
[ C o ( N H 3 ) s O N O ] C I 2, prepared by means of wet
chemical methods and by means of a photochemical
isomerization process, in order to determine whether
i.r. spectroscopy can throw more light on the struc-
tural differences between the compounds.
905
[Co(NH3)sNO2]CI 2 and [Co(NHa)sONO]CI 2 were syn-
thesized according to the methods given by JOHNSON and
PASHMAN [9]. {-Co(NHa)5ONO]CI 2 was also photochemi-
cally prepared by irradiating f C o ( N H 3 ) s N O 2 ] C I 2 with u.v.
light (350 nm).
The i.r. spectra were obtained using a Bruker 113V FT-IR
spectrometer. The spectra were recorded in the form of KBr
or polyethylene discs. In the case of the photochemical
nitro -, nitrito reaction, the KBr disc containing the nitro
compound was irradiated with u.v. light (350 nm) and the
disc was removed for very brief periods from under the light
to record the spectra. In the case of the i.r. spectra the samples
were cooled to liquid nitrogen temperatures in an Oxford
Instruments CF 1100 A continuous flow helium cryostat.
RESULTS
(a) Rates of isomerization
The i.r. spectra of [Co(NH3)sNO2]C! 2 and freshly
and photochemically prepared [ C o ( N H a ) s O N O ] C I 2
are summarized in Table 1. The diffeqmces in the i.r.
spectra between the nitro and nitrite compounds have
been fully discussed in various studies [10, 11].
When [Co(NH3)sNO2]C12 is irradiated with u.v.
light, two bands at 1460cm -1 ( v , N = O ) and
1055 c m - 1 (v,NO) appear, amongst other features, in
the i.r. spectra. These features signify the formation of
[Co(NH3)5ONO]CI 2, and their intensities have been
recorded at regular time intervals. These results are
summarized in Tables 2 and 3. The fraction of
nitrite present in the sample at any given time t can
be obtained from the results in Tables 2 and 3.
The variation of the concentration of
[ C o ( N H 3 ) s O N O ] C I 2 (as measured by the intensity of
v , at 1460 c m - 1) with time when [Co(NH3)sNO2]CI 2
is irradiated, is shown in Fig. 1. The graph of In
[1/(1 - Z p ) ] vs time for vu(N=O) is a straight line (Fig.
2) and the reaction can therefore be classified as a first
order one of the form (1-Xp) = e -kt or X, = e -kt where
Xr is the fraction of reactant, k is calculated to be equal
to 2.53 +0.05 x 1 0 - 4 s - 1 for the photoisomerization
of [Co(NH3)sNO2]CI 2. After completion of the reac-
906 A. M. HEYNS and D. DE WAAL

Table 1. The i.r. bands in [Co(NHa)sNO2]CI 2 and in freshly and photochemically prepared
[Co(NHa)sONO]CI 2

[Co(NHa)sNO2]CI 2 [Co(NHa)sONO]CI 2 Photochemically

prepared
[Co(NHa)5ONO]CI2
Assignment Assignment

3270 s v,(N-H) ~3260s VNn~ 3270 S

3190 sh v,(N-H) 3180 sh 3190sh
1615 s firth3 1620 s finn3 1610 S
~ 1575 sh 6,s(NH3) 1460vs v,,(N=O) 1460vs
1428 vs v,(NO2) 1454 vs
1365 w v,(NO2)
1330 sh 1320sh
1310 s 6,(NH3) 1315 s 6Nn~ 1315 s
1285 sh 1270 sh 1292 sh
1225 sh 1225 sh
1180 w 2 590 m

1055 vs vdN--O) 1055 vs

845 s pr(NH3) 850 s pr(NH3) 853 s
843 s
822 vs 6,(ONO)
730 sh 740 sh -- 735 sh
590 s pw(NO2)
510 sh vCONH3
490 m
485 m 488 m vCoNm 488 m
428 s
376 m M- NO2
347 m skeletal 339 m skeletal 341 m
deformation deformation
317 sh 6N_CO_N 307 w 6N-CO-N 308 W
300 S pr(NO2) t
260 W vCo-0(ONO) 274 w
275 w 228 w 258 w
177 m Skeletal
deformation
125 s Lattice mode 157 Lattice mode 158
139

Table 2. Appearance of the v~,(N=O) band at Table 3. Appearance of the v,,(N-O) band at
. U.V. 1055 c m - 1 in the reaction
1460 c m - 1 in the reacUon [Co(NH3)sNO2]CI2 u.v.

[Co(NH3)sNO2]CI 2 ---,[Co(NH3)5ONO]CI 2
[Co(NH3)sONO]CI2

No. t(s) Zp In[l/(1 -Zp)] No. t(s) Xp In[l/( 1 --Xp)]

1 0 0.087 0.091 1 0 0.116 0.123

2 358 0.242 0.277 2 313 0.386 0.488
3 659 0.345 0.423 3 626 0.474 0.642
4 1079 0.445 0.589 4 1096 0.582 0.872
5 1560 0.526 0.747 5 1566 0.655 1.064
6 2340 0.614 0.952 6 2349 0.757 1.415
7 3238 0.692 1.178 7 3289 0.810 1.661
8 3719 0.729 1.306 8 3758 0.834 1.796
9 4440 0.773 1.483 9 3915 0.881 2.129
10 5459 0.822 1.726 10 5481 0.907 2.375
11 6359 0.857 1.945 11 6420 0.927 2.617
12 7019 0.883 2.146 12 7047 0945 2.900
13 8398 0.903 2.333 13 9396 0.989 4.510
14 9419 0.935 2.733 14 10336 0.992 4.828
15 10259 0.947 2.937 15 11119 0.998 6.215
16 11 159 0.958 3.170

tion the well-known s p o n t a n e o u s nitrito ~ nitro iso- i s o m e r i z a t i o n of freshly a n d p h o t o c h e m i c a l l y pre-

m e r i z a t i o n reaction was s t u d i e d by r e c o r d i n g the pared [ C o ( N H 3 ) s O N O ] C 1 2 . T h e rate c o n s t a n t so
intensities of vs(N-O) at 1055 c m - t at regular time d e t e r m i n e d is equal to 1.43 +_0.02 x 10 - 6 s - 1 which
intervals. T h i s was d o n e to c o m p a r e the rates of c o m p a r e s very well with t h e value o b t a i n e d by ADELL
 An i.r. study of nitro-nitrito linkage isomerization 907

II

0'8

"--V"
0.6

Xp
0-4

0'2

I I I I 1 1 I
mOO 1600 1400 1200 I000 800 600
Q I I I I I I ~- lcm-l)--
0 2 4 6 8 I0 12
t XI 0 - " IS) Fig. 3. The i.r. spectra of [Co(NH3)sONO]CI2 in the fre-
quency range 400-1800 cm-1. The bottom spectrum is that
Fig. 1. The fraction ofnitrito groups present at time t for the of a freshly prepared sample and the top one represents a
hv photochemically prepared sample.
reaction [Co(NH3)sNO2]C12 ~ [Co(NH3)sONO]CI~.

1460 cm-1, while it is split into peaks at 1460 and

4 1454 c m - 1 in freshly prepared samples. The N and O
3
I is possible. However, the same applies to photo-
9 I I I I i
0 2 4 6 8 I0
txlO-3(s)
Fig. 2. Obedience of the kinetic data of the reaction
hv
[Co(NH3)sNO2]CI2--*[Co(NH3)sONO]CI2 to the first or-
der rate law 1-Xp= e -kt.
[3] and that of HOHMAN I'7]. This dearly demon-
strates that the spontaneous nitrito--* nitro isomeriz-
ation is identical for photochemical and freshly pre-
pared samples of [Co(NH3)sONO]CI2. It is also
evident from the above results that the rates
of the photochemical nitro - , nitrito isomerization
(tl/2 = 49 rain) and the spontaneous n i t r i t o ~ n i t r o
isomerization (t 1/2 = 6 days) are significantly different.
The i.r. spectra of the photochemically prepared and
freshly prepared samples of 1'Co(NH3)5ONO]CI 2 are
very similar, as can be seen in Fig. 3. However, a closer
scrutiny of these results reveals the following:
It is very difficult, or even impossible, to prepare
[Co(NH3)sONO]CI2 photochemically in an absolute
pure state without traces of N O 2 impurities. This can
be seen by the presence of extremely weak i.r. peaks
due to the N O 2 groups, even after irradiating the
samples for several weeks.
vu(N---O) in photochemically prepared
[Co(NHs)sONO]CI2 is a strong, sharp band at
atoms all lie in general positions in the crystals of
[Co(NH3)sONO]CI 2 under P21nb (C9v) symmetry
1"81, and the N = O and N - O stretching modes can
each split into Al(i.r., R)+A2(-)+BI(i.r.,R)+B 2
(i.r., R) components. It is unlikely that all of the factor
group components will be resolved in the i.r. spectra
but it can at least be said that a splitting of these bands
chemically prepared [Co(NH3)sONO]CI 2 and it is
J not clear at this stage why a splitting is observed in
12 only one of the modifications.
The mode 6,(NH3) is of AI symmetry for the "free"
molecule of C3v symmetry and can theoretically split
into four factor group components under the C9v
space group for [Co(NH3)5ONO]CI 2. However, there
are five different NH 3 groups with N - H bond lengths
varying between 0.65-1.23 A [8] and it can be ex-
pected that different i.r. components of this mode will
be resolved. It is evident in Fig. 3 that at least four
components of 6,(NHa) can be detected at 1320 sh,
1315, 1270 and 1225cm -1 in freshly prepared
[Co(NH3)5ONO]C12. The shoulder at 1320 c m - 1 is
not present in the photochemically prepared sample;
the broad shoulder at 1225 c m - 1 is much weaker and
the component at 1270cm-1 has shifted to
1292 cm-1. This latter band is very characteristic of
photochemically prepared [Co(NH3)sONO]CI 2 and
can be used for identification purposes.
p,(NH3), which occurs at 850 c m - 1 in
[Co(NH3)sONO]CI 2, is split into two components at
853 and 843 cm -1 in photocbemically prepared
[Co(NH3)sONO]CI 2 and is once again very charac-
teristic of this compound, p~(NH3) is of E symmetry
and will split into 2A in the C 1 site group symmetry
that the N H 3 groups occupy in the crystal lattice. One
must, however, bear in mind that there are five
different N H 3 groups in the crystal so that extensive
splitting of this band is theoretically possible.
908 A.M. Hr~vtqsand D. DE WAAL
f disorder existing in these crystals during the iso-
I I I I I I I I I
380 3 4 0 3 0 0 260 220 180 140 I00 60
_- ~cm-i I
Fig. 4. The far i.r. spectra of (a) [Co(NH3)sNO2]CI2 at
300 K; (b) [Co(NH3)sNO2]C12 at 83 K; (c) freshly prepared
[Co(NHa)5ONO]CI2 at 300K; (d) freshly prepared
[Co(NHa)sONO]CI2 at 83 K; (e) photochemically prepared
[Co(NHa)sONO]CI2 at 300 K; and (f) photochemieallypre-
pared [Co(NH3)sONO]Ci2 at 83 K.
The remaining NHa vibrational modes are broad,
and reveal no splitting, with the result that very little
can be concluded as far as the structures of the
different complexes are concerned.
The far i.r. spectra of [Co(NH3)sNO2]C12 and
[Co(NH3)sONO]CI 2 prepared in two different ways
are shown in Fig. 4. The far i.r. spectrum of the former
at ambient temperatures has already been reported
[12,1 and an assignment of the bands has been made
with the aid of a normal coordinate analysis. The
tentative assignment of bands given in Table 1 has
partly been based on these results as far as
[Co{NHa)sNO2]CI 2 is concerned and has also been
done by comparing these results with those obtained
on the two [CofNH3)sONO-IC12 compounds.
The far l.r. spectrum of freshly prepared
[Co(NH3)sONO,1C12 reveals sharper and better-de-
fined absorption peaks than those observed in the
photochemically prepared sample. This most prob-
ably serves as an indication that the sample prepared
by chemical methods has more ordered structure than
the one obtained by photochemical methods. There
are also some differences with regard to the number of
bands and the frequencies of some of these bands.
It is evident from Fig. 4 that the lattice mode ob-
served at 157 cm-1 is split into two components at
158 and 139crn -1 in photochemically prepared
[Co(NH3)sONO]CI 2. A rather prominent ab-
sorption peak at 228cm -~ in freshly prepared
[Co(NHa)5ONO,1CI2 a t - 190C is also absent in the
spectrum of the photochemically prepared sample.
Furthermore, the band assigned to a C o - O N O stret-
ching mode at 260 cm- 1 in freshly prepared samples is
split into two components in the photochemically
prepared crystals. The far i.r. spectra of the inter-
mediate product [Co(NH3) (ONO)l/2(N02)I/2"]C12
were featureless and very little, if anything, could be
concluded from these spectra. This is indicative of
merization process.
The structure of [Co(NH3)5ONO-ICI2 consists of
cations and anions arranged in a fluorite-like arrange-
ment held together by a network of hydrogen bonds
and electrostatic forces [8,1. The structure of
[Co(NHa)sNO2,1CI 2 can also be regarded as a slightly
distorted fluorite structure [ 11-1. The frequency shifts
in the lattice modes which occur between the nitro and
nitrito complexes indicate that there are, however,
distinct differences in these forces holding the cations
and anions together in these complexes.
[Co(NHa)sNO2,1CI 2 which was freshly prepared by
means of wet chemical methods sometimes showed
absorption peaks at 1040 cm -1 with a weak and
broad shoulder at 1055 cm-1. The nitro complexes
obtained by the isomerization of the nitrito complexes
invariably showed these absorption peaks. These are,
of course, indications of the presence of ONO impu-
rities in the lattice of [Co(NH3)~NO2]CI 2. In some
other samples the absorption maximum is at
~ 1055 cm-1 with a weak shoulder at 1040 cm-1,
showing that there are two orientations possible for
the O N O - ion in the lattice of [Co(NH3)sNO2]C12.
The population of these orientations is apparently
statistically controlled and can vary in different sam-
ples under different conditions. As soon as the sample
is irradiated and partial isomerization of the N O r to
O N O - has occurred, a single absorption peak is
obtained. Results which have been obtained with a
sample that exhibited weak absorption peaks at 1055
and 1040era -1 and which has subsequently been
irradiated, are shown in Fig. 5. The bands that are
shown in Fig. 5a occur at 1190 cm -1 (2 5 9 0 - 2
x p,,(NO2)), at ~ 1100 em -1, 1055 sh and 1040 cm -1
(v,N-O), 845 cm- 1 (pr(NH3)) and 822 cm- 1
(iS, (ONO)). These represent the characteristic vibra-
tions of [Co(NH3)sNO2]C12 in this frequency range,
d
I I I I I I I I
II00 900 II00 gO0 I10O ~ I100
;cm-II--
Fig. 5. The i.r. bands of ONO- impurities at 1040 and 1055
(sh) era- 1in [Co(NH3)sNO2]CI2 shown in (a). Upon irradia-
tion, only one band is shown at 1055 cm- ~ is observed (b)
after 360 s; this band grows in intensity after 480 s as is shown
in (c) and after 960 s a strong band is observed at 1055 em- i
while the t5S (ONO) band at 822 ~,an-1 has disappeared
completely (d).
 An i.r. study of nitro-nitrito linkage isomerization
as well as the vs(N-O) components of O N O - impu-
rities. The absorption peak at 1040 crn-1 gradually
shifts upwards upon irradiation with u.v. light until an
equilibrium value at 1055 cm -1 is obtained. This
points to a gradual strengthening of the N - O bond
during the isomerization process. At the very low
concentrations of the nitrito complex in
[Co(NH3)sNO2]CI2 mentioned above a solid sol-
ution is expected to be formed, and a splitting of the
v, (N-O) band into two components can only be
explained in terms of two different O N O - groups in
the lattice of the [Co(NHa)sNO2]CI2 crystal. In this
crystal, the Co, NH 3 and NO z groups are supposed
to occupy positions of C2 symmetry under the
space group of C2/c [9]. The symmetry of C2 is
incompatible with the C3v symmetry of the
"free" NH a groups, and if one NH 3 group occupies
a site of this symmetry in the crystal then the
orientations of its hydrogen atoms must be dis-
ordered. It appears from the splitting of the
v~(N-O) band of the O N O - groups in solid solutions
of the [Co(NH3)sNO2]CI 2 crystal as if the structure
determined for this crystal could possibly be in error
since, if the symmetry of the [Co(NHa)sNO2] 2+ unit
of C2 symmetry is lowered when O N O - groups are
gradually replaced by NO~ groups, it will be lowered
to C1. These [Co(NH3)sONO] 2+ groups which are of
very low concentrations can then occupy the equival-
ent C~sites in the [Co(NHa)sNO2]CI2 crystal and no
splitting of bands is expected to occur. If the symmetry
of the [Co(NH3)sNO2]CI2 crystal is equal to Cc(C~)
with Z = 4, then there could be two different sets of
cations of C~ symmetry since the only positions
available under this symmetry are two equivalent
positions of C1 symmetry. However, two different sets
of cations in the nitro-complex must also be reflected
in the i.r. bands of the nitro group. Some of the NO2
bands in freshly prepared [Co(NH3)sNO2]CI 2 are
split, however, this could also be due to a factor group
splitting of bands predicted by the C2/c [9] space
group suggested for this compound.
In addition to these two components of v(N-O) of
the solid solution of [Co(NH3)sONO] 2+ in
[Co(NH3)sNO2]Ci2, a broad, weak and very diffuse
absorption maximum at ~ 1100 cm -~ can also be
discerned in this frequency range (Fig. 5). This feature
disappears at higher concentrations of the nitrito
909
groups and suggests that more orientations of the
ONO groups might be possible in the early stages of
the isomerization process. It was suggested by
JOHNSON and PASHMAN[13] that a bidentate metast-
able transient occurs in the solid state photolysis of
[Co(NHa)sNO2]CI 2 at liquid nitrogen temperatures.
f o/\\1,.
0
[(NH==)sCo-NOz] 2+ ~ NH~)sC N
[(NH a)sCoONO]2+
The formation of such an intermediate will of cause
have a profound effect on the N - O stretching modes in
particular and the broad band at ~ 1100 cm- i could
possibly indicate the existence of such a transient. This
also explains the fact that the band disappears during
the later stages of the photochemical isomerization
process as is evident in Fig. 5.
Acknowledgement--The authors wish to thank the Council of
the University of Pretoria and the Foundation of Research
Development, CSIR, Pretoria, for financial support.
REFERENCES
[1] B. ADELL,Z. anoro. Chem. 252, 272 (1944).
[2] B. ADELL,Z. anorg, allo. Chem. 271, 49 (1952).
[3] B. ADELL,Z. anorO. allo. Chem. 279, 210 (1955).
[4] R. G. PEARSON,P. M. HENRY,J. G. BERGMANNand
F. BASOLO,3. Am. chem. Soc. 76, 5920 (1954)
[5] I. R. BEA'FrlEand D. P. N. SATCHELL,Trans. Faraday
Soc. 52, 1590 (1956).
[6] W. W. WENDLANDTand J. H. WOODLOCK,J. inorg.
nucl. Chem. 27, 259 (1965).
[7] W. H. HOHMAN,2. Chem. Educ. 51, 553 (1974).
[8] I. GRENTHEand E. NORDIN, Inorg. Chem. 18, 1869
(1979).
[9] O. B6RTIN,Acta chem. scand. 22, 2890 (1968).
[10] R.B. PENLAND,T. J. LANEand J. V. QUAGLIANO,J. Am.
chem. Soc. 78, 887 (1956).
[11] K. NAKAMOTO,J. FUJITAand H. MURATA,J. Am. chem.
Soc. 80, 4817 (1958).
[12] I. NAKAGAWAand T. SmMANOUCm,Spectrochim. Acta
23A, 2099 (1967).
[13] D. A. JOHNSONand K. A. PASHMAN,Inor O. nucl. chem.
Lett. ii, 23 (1975).