JOURNAL O F T H E

AMERICAN CHEMICAL S O C I E T Y
(Registered in U. S. Patent Office) (0Copyright, l9j6, by t h e American Chemical Society)

VOLUME78 MARCH 6, 1956 NUMBER

5

PHYSICAL AND INORGANIC CHEMISTRY

[CONTRIBUTION FROM THE DEPARTMENT
OF CHEMISTRY O F THE UNIVERSITY O F S O T R E DAME]

Infrared Absorption Spectra of Inorganic Coordination Complexes. VII. Structural

Isomerism of Nitro- and Nitritopentamminecobalt(111)Chloridesla~h
B Y R. B. PENLAND,
T. J. LANE^^ AND J. v. QUAGLIANO
RECEIVED
SEPTEMBER
21, 1955

Infrared spectra of nitropentamminecobalt(II1) chloride and nitritopentarnrninecobalt( 111) chloride in the solid state
have been measured. Spectral evidence is presented to support the conversion .of nitritopentamminecobalt( 111) chloride
to nitropentamminecobalt( 111) chloride. In the spectra of these complexes the deformation vibration frequencies of the
SHa ligand, degenerate, symmetric and rocking are identified. The remaining absorption bands in the region from 1700 to
650 (5.8-15 p ) can be assigned to the nitro and nitrito frequencies. Changes in the spectrum of the nitritopentam-
minecobalt(II1) ion with regard t o intensity of certain bands with time are significant. Bands which show such changes in
absorption are assigned to those parts of the complex which are responsible for nitrito and nitro vibrations. By comparison
of the spectra of the pure nitro and the freshly prepared nitrito isomers, the bands that decrease in intensity can be assigned
to the nitrito group, while those new bands that appear and gradually increase in intensity can be assigned to the nitro
group.
Introduction Lecomte and Duval. Infrared spectra of pow-
Structural isomerism arises when one or another dered samples of the pentammine compounds have
atom in a coordinating group ligates to the central also been determined by Lecomte and Duva13 who
metal atom of a coordination complex. In the assigned some of the observed bands in the nitro
complex ions nitropentamminecobalt(II1) and ni- isomer and concluded that the complex exists only
tritopentamminecobalt(III), the seat of isomerism in this form.
is the -NO2 ligand which may be present in the co- In this paper are reported infrared spectra of
ordination sphere in the nitrito form (Co-ONO) or these complexes in the solid state, changes in the
in the more stable nitro form (Co-N02). Two infrared spectra associated with the rearrangement
isomers of nitropentamminecobalt(111) chloride of the nitrito complex to the corresponding nitro
have long been known, an unstable red form which compound, and assignments of the infrared bands
transforms into a yellow-brown form either in solu- in both the nitro and nitrito isomers in the sodium
tion or in the solid state. On the basis of the colors chloride region.
of these complexes the unstable red form was as- Experimental
signed as the nitrito and the stable yellow-brown
Nitropentamminecobalt(II1) chloride and nitritopentam-
form as the nitro isomer. The kinetics of the re- minecobalt(II1) chloride were prepared by the method of
arrangement of nitrito complexes to the corre- Walton . 4
sponding nitro compounds have been extensively Anal. Calcd. for [Co(NH3)5N0~]C12: NH,, 32.63.
studied in aqueous solution.2 Found: NH3,32.75. Calcd. for [Co(NHa)50SO]Clp: " 8 ,
DebyeScherrer X-ray patterns and ultraviolet 32.63. Found: NHs. 32.80.
spectra3 of these complexes have been studied by Absorption Measurements.-The infrared spectra were
obtained by means of a Perkin-Elmer infrared spectro-
(1) (a) Paper VI in series, THISJOURNAL, 77, 6521 (1955); (b) photometer model 21 using a sodium chloride prism. Spec-
Presented before t h e Pittsburgh Conference on Analytical Chemistry tra of samples, obtained by the potassium bromide disk
and Applied Spectroscopy, Pittsburgh, Pa., Feb.. 1955. Supported in technique and checked in Nujol mulls, were measured a t
part under A E C Contract -4t(ll-l)-38, Radiation Project of t h e Uni- consecutive time intervals until no further change was
versity of Notre Dame; (c) Reverend Thomas J. Lane, C.S.C. observed. Experimental details are the same as reported
( 2 ) B. Adcll, Svensk Kem Tid., 66, 318 (1944); 67, 260 (1945); in a previous communicatioii.5
Z . anovg Chern., 252, 2 7 2 (1944); 271, 49 ( 1 0 5 2 ) ; A c t a . Chetn. Scand..
1, 624,659 (1947); 4, 1 (1950); 6, 54, 941 (1951); F. Basolo, B. D. (4) H. F. Walton, "Inorganic Preparations," Prentice-Hall, Inc.,
Stone, J . 0. Bergmann a n d R. G. Pearson, THISJOURNAL, 76, 3079 New York, N. Y., 1948,p. 92.
(1954). ( 5 ) J. P. Faust and J. V. Quagliano, THISJOURNAL,76, 8346
(3) J. I.eri,inte .ind C1 I ) u \ : * l , Ijull ipic ' h i i n . , 12, li78 ( l ! l i 5 ) (19.54).

SSi
 Results
In Fig. 1 are given the infrared spectra of freshly
prepared nitritopentamniinecobalt(II1) chloride,
this isomer aged for five days, and pure nitropent-
amminecobalt(II1) chloride. The spectra of hex-
amminecobalt(II1) chloride aiid sodium hexanitro-
cobaltate(III), used to assist in the assignment of
NH3 and NO2 vibrations, were reported in a previ-
ous communication.j
Discussion
Nakagawa aiid IlIizushima' have calculatetl
Yarious deformation vibrations of the CH, group
in organic molecules. The vibrations of the NH::
ligand as a whole can be considered quite similar to
the CH3 vibrations and the normal modes of the
deformation vibrations of the NH3 ligand in metal
coordination coniplexes have been calculated and
have been shown to be in good agreement with the

100*. 1500
Wave N u m b e r s in cm -'
I300 1200 1100 1000 950 900 850
I '
observed infrared frequencies8 By inspection of
the spectra of many metal ammine complexes, the
three bands observed a t about 1600 cm.-', about
1320 cm. -' and about 850 cm. have been identi-
fied with the degenerate deformation vibration,
symmetric deformation vibration and rocking
vibration of NH3ligands, respectively.
In this study we can easily identify the ligated
KHa deformation vibrations from the frequency
values as well as from the shapes of the corre-
sponding absorption bands. In both the nitro
and nitrito isomers the peak observed at 1595
U I
cni.-' (6.3 p) is assigned to the 3"
ormation; the peaks a t 1313 em.-' (7.6 p) and
degenerate def-
6 7 8 9 10 II 12
132.7 cni.-' (7.63 p) are assigned to the NH3 sym-
Wave L e n g t h i n Microns
nieteric deformation of the nitro and nitrito iso-
Fig 1.-Infrared absorption spectra of the complexes : mers, respectively, and the peak a t 850 cni. -I
--, nitropentamminecobalt( 111) chloride, [Co( KH8)6NO2]- ( 1 1 .S p) is assigned to the NH3 rocking for both
CI?, ----,nitritopentamminecobalt(II1) chloride, [Co("a)$- complexes.
OKO]Clz, freshly prepared; . , . . . ., nitritopentammine- The absorption bands in the region from 2000-
cobdlt(II1) chloride, [Co(SH3)sONOI(212, aged. 6.50 ern.-' remaining to be assigned are associated
with vibrations of the NO2 and O N 0 ligands, for
In the 3 ,i.iregion peaks are observed for both the it has been shown that cobalt-nitrogen stretching
nitro and nitrito isomers a t 3200 em.-' and these frequencies are not expected to appear in this re-
compare with the peak a t 3130 cm.-l of hexam- g i ~ n . On ~ aging the sample of [Co(SHa)jONO]-
minecobalt(II1) chloride, assigned to ?;-H stretch- C12, the spectra show bands which can be assigned
ing vibrations. The shift in the N-H stretching to the nitro ligand; those very strong bands which
frequency in the 3 p region of XH3 on coordination decrease in intensity can be assigned to the nitrito
is in accord with the results of the extensive studies ligand, arising from rearrangement of the nitrito
of ammine complexes reported.G complex to the corresponding more stable nitro
The spectra of both isomers reveal absorptioii isomer. Those bands at 1430, 1315 and 823 C I I ~ . - - '
maxima a t 1595, about 1315 and 850 cm-I. These which increase in intensity are assigned, from a
are well-defined absorption bands and have coli- coinparison with the values reported for the hexa-
tours which correspond to those observed in the nitrocobaltate(II1) ion, simple nitrites and organo-
spectrum of [CO("~)G]C~~.~ I n addition to these nitro compounds,j to antisymmetric stretching,
characteristic frequencies common to the spectra symmetric stretching and deformation vibrations,
of metal ammine complexes, the spectrum of the respectively, of the nitro ligand. Similarly, bands
nitrito isomer has two additional peaks, observed of decreasing intensity in the spectra of [CO(NH?)~-
a t 1460 and 1065 cm.-l. On aging, the sample of ONO]Clza t 1430 and 1063 c m - l may be assigned
the nitrito isomer shows a spectrum in which these to the two O N 0 stretching vibrations. The 1460
bands decrease in intensity and simultaneously two cm.-l band assigned to the CoONO stretching vi-
new bands appear at 1430 and &25 cm.-l (Fig. 1). bration appears a t a higher frequency than that
These bands which increase in intensity are charac- assigned to the nitro ligand. allso,iii the spectrum
teristic of the nitro complex as seen by a comparison of the freshly prepared nitrito isomer, a slight
of the spectrum of sodium hexdnitrocobaltdte- shoulder present a t 1430 cm.-' indicates that ;t
(III).O X gradual change in the shape of the spec- trace of the nitro isomer is present in the sample.
trum from the nitrito to the nitro isomer is ob- On aging the sample of [ C O ( X H ~ ) ~ O S O ]the C~Z,
served for the unstable nitro complex in Nujol and absorption band in the 1430 cm-l region, which
also when present in a pressed potassium bromide appears to shift to a lower frequency, has been
disk. Xbsotptiori spectra of nitritopentammineco- resolved into two sharp bands, m e a t 1.100 cm.
balt(II1) chloride, ground, and aged in Nujol, were and the other a t 1430 cm.-l (Fig. 1). The band at
similar to the spectra of samples aged in potassium the higher frequency decreases in intensity on ag-
bromide disks, and no evidence of interaction be- ( i ) I. Nakngawa a n d S . l l i z u i h i m a , 1;iill. C l i ~ r u .Soc. Jubnir. iii

tween the sample and potassium bromide was press.

( 8 ) S .\Iizushima, I . Nakagawa a n d J V , Qi~agliano,J C'iiriii. P h y r . ,
found.
(I;) G Is i\ LLoi C Ciiiriii iii(1 I \ lJii~,liiiio l i i r i Tc)i IKUII my, I S a k ~ k a n , 5~ , R I i i i i . i l i i i i i l i iaiid J . \ - ! J ~ i : < ~ I i : i u ~ t
77, 0 1 i')
(1'125) 'I 1 1 1 5 J O I ~ K R I I .77,
. 88!l (I'l>.>)
Ifarch 5 - 1933 NORMAL
VIBRATIONSOF TETR~WY.~NOPLATINATE(~~)
ION 889

ing and finally disappears completely. The as-
signment of this band to one of the nitrito stretch-
ing frequencies seems reasonable. The band a t
1430 cm.-', however, grows in intensity on aging
the sample. ,ki described above, this band is iden-
tified with the unsymmetrical stretching vibration
of the nitro ligand.
In the spectrum of [Co(hTH3)&TO2]Clz, the
broad shouldered absorption band with a peak a t
1315 cm.-' results from an overlapping of the two
peaks previously assigned to the symmetric nitro
and the symmetric ammonia vibrations. X com-
parison of the spectrum of [Co(XH3)5r\;02]Clz with
the superposition of the spectra of Xa3[CO(NOz)~]
and [Co(NH&]C& which show absorption bands
a t 1338 and 1333 a n - ' , respectively, makes this
evident. Only a single relatively sharp band, how-
ever, appears in this region for the freshly prepared
nitrito complex. It has been shown that the ni-
trito isomer on standing several days a t room tem-
perature gives rise to an absorption spectrum al-
most identical with the spectrum of the pure nitro
compound. This experimental result can be ex-
plained as a change in the cohrdinating group from
(Co-ONO) to (Co-hTO2).
SOTRE
DAME.INDIASA

[CGNTRIBUTIGN FROM TWE DEPARTMENT

OF CHEMISTRY, U N I V E R S I T Y OB YOTRE D A M E ]

Infrared Absorption Spectra of Inorganic Coordination Complexes. VIII. Normal

Vibrations of Tetracyanoplatinate (11)Ion1
B Y D. 5 2 . S T V E E NICHIRO ~ [ I Z U S H I M A ' ~ h N D J. \'. QUAGLIANO
Y , ~ ~ NAXAGAWA, SAN-ICHIRO
RECEIVED
APRIL 6, 1955

The infrared absorption spectra of potassium tetracyanoplatinate(I1) have been recorded over the range from 2 to 40 p .
In addition to the characteristic peak observed a t about 2100 cm.-', there were observed several peaks in the low frequency
region. The frequency values of these peaks, together with those of the known Raman lines in the same region, can be
brought into good agreement with the values of the calculated normal frequencies of the complex cyanide ion. The cal-
culation was made as a nine-body problem on the basis of the Urey-Bradley field.

Introduction
An understanding of the nature of the metal-
ligand bonds in complexes is of fundamental sig-
nificance in the study of coordination compounds.
Investigations of the infrared absorption of metal
cyanide complexes offer an interesting problem in
this field, since these compounds are expected to
show relatively simple spectra. Specifically, cya-
nide frequencies are present a t about 2100 cm. -l,
but no other fundamentals would be expected to
appear until the KBr region, where the metal to
ligand bond frequencies appear in the vibrational
spectra. That such is actually the case may be ex-
pected from the Raman studies of Mathieu3 who
calculated only the AI, vibration of the skeleton.
Later, this calculation of skeletal motions was im-
proved by Maccoll, using the modified valence-
force field but still regarding C=N as a dynamical
unit. However, the nine-body calculation is not
very difficult and, as has been shown in previous pa-
p e r ~the
, ~ Urey-Bradley field is much more suitable
to explain the vibrational spectra of such a rnole-
cule. Therefore, the normal frequencies were cal-
culated as a nine-body problem using this field,
and the computed frequencies have been compared
with those obtained in the present investigation, in
the region from 5000 to 250 cm.-' (2 to 40 p ) .
(1) For paper VI1 in this series see THISJOURXAL, 78, 887 (1956)
(2) (a) Presented in part before t h e 126th meeting of the American
Chemical Society, September, 1954. Supported in part under A E C
Contract AT(l1-1)-38, Radiation Project of t h e University of h'otre
Dame. Abstracted in part from t h e P h . D . Thesis of D. M. Sweeny,
Notre Dame, 1955. (b) Visiting Professor, from the Faculty of Science,
University of Tokyo.
(3) J . Mathieu, J. chim. $hys., 36, 308 (1939).
(4) A. Maccoll, Proc. R o y . SOC.N.S.W., 77, 130 (1943).
(5) T. Shimanouchi, J . Chem. Phys., 17, 245, 7 3 4 , 848 (1949);
see also reference 12.
Experimental
Preparation of Compounds.-Potassium tetracyanoplat-
inate (11) trihydrate, K2Pt( CN)r,3HnO, was prepared ( a )
according to the method of h'Ieillet.6
The analysis was carried out on sample dried in at1 Abder-
halden drier a t 110" for 3 days. Anal. Calcd. for KnPt-
( C N ) 4 . 3 / j H 2 0 : C, 12.51; S, 14.56. Found: C, 12.46; iY,
14.56.
( b ) The compound was also prepared according t o the
method of Claus.? This preparation gave a product spec-
troscopically identical with that of the analyzed sample
(a). In the region of the OH stretching frequency some
slight differences exist which probably are attributable t o
different degrees of hydration in the two samples investi-
gated.
Absorption Measurements.-Spectra were obtained by
means of a Perkin-Elmer, model 21, infrared spectropho-
tometer, using CaFa, riaC1, KBr and CsBr prisms. Prepa-
ration of potassium bromide disks was carried out according
to the direction of Stimson and O'Donnell.s The disks were
used for observation in the region of 2 t o 24 p, and the re-
sulting spectra were checked using Nujol mulls of these
compounds. I n the spectrum of K I P ? ( C N ) ~ . ~ Hobtained
ZO
by the potassium bromide disk technique a few absorption
peaks were observed in the region between 1500 and 600
cm.-' which should not appear according t o our calculations.
The positions and intensities of these peaks depend upon the
previous history of the sample. I t has been possible to dem-
onstrate that these absorption peaks are due t o the water
of crystallization and can be avoided by dehydrating the
material a t 197" i n vacuo. Unusual optical behavior of
hydrated planar Pt(CN)a= complex compounds has been
r e p ~ r t e d . ~ ,Tetrahedral
'~ metal cyanide complexes examined
in this Laboratory do not show these additional absorption
peaks.
Beyond 24 fi the Nujol mull technique was employed;
however, KBr disks can be used conveniently up to about
32 p .
( 6 ) A. Meillet, J . Pharm. Chim., [31 3 , 444 (1843).
(7) C. Claus, A n n . , 107, 132 (1855).
(8) M. M. Stimson and M. J. O'Donnell, THISJ O U R N A L , 74, 1805
(1952); see also J. P. Faust and J. V. Quagliano, i b i d . , 76, 5346 (1954).
(9) L. A. Levy, J . Chem. SOC.,93, 1446 (1908).
(IO) S. Yamada, Bzdl. Chem. SOL.Japan, 24, 125 (1951).