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lntroduction to lnorganic

Infrared Spectroscopy*
John R. Ferraro
Argonne National Laboratory
Argonne, Illinois

The infrared spectroscopic study of organic compounds has been


known for a number of years. However, the application to inorganic
compounds had a rather late start. Most of the early work on the
spectra of inorganic compounds concerned itself with the Raman
method. Some reflection infrared methods [1 ] were used as early as
1930. The Iack of high-resolution spectrophotometers, plus the fact
that adequate specimen preparation was difficult, delayed progress in
this field. Since large particle size gave considerable scattering loss-
es, most early infrared spectra of inorganic compounds gave broad,
indeterminate absorptions as compared to the sharp spectra obtained
with organic compounds.
With the introduction of commercial high-resolution spectropho-
tometers and new methods of specimen preparation, such as Nujol
mulls, pressed disks [2 - 4 ], film techniques, and the recently rare-
gas matrix isolation method [5 ], the spectra obtained were found
to be excellent. Revival of interest in inorganic compounds took
place. Lecompte must be given credit for a considerable amount of
this revival. He and his co-workers examined numerous inorganic com-
pounds, the studies appearing in a series of papers in 1951 [6 ' 7 ]. A
very important paper by Miller and Wilkins [8 ], which added fur-
ther impetus to this revival, appeared in 1952. They examined the

*Based on work per.fonned under the auspices of the U.S. Atomic Energy Commission.

35

H. A. Szymanski (ed.), Progress in Infrared Spectroscopy


© Springer Science+Business Media New York 1962
36 John R. Ferraro

spectra of over 150 salts, and their correlation for analytical and
identification work proved excellent. The last nine years has seen
a tremendous development in the progress in inorganic infrared spec-
troscopy.
It is the purpose of this paper to point out some of this de-
velopment, with particular emphasis on the application of infrared
spectroscopy to solving various problems in inorganic chemistry.
The paper is in no way intended to be a complete bibliographical
report on this subject, but attempts to serve only as an introduction.

QUALITATIVE AND QUANTITATIVE ANALYSIS


OF INORGANIC COMPOUNDS
WITH INFRARED SPECTROSCOPY
It is beyond the scope of this paper to present elaborate details
concerning the qualitative and quantitative analysis of inorganic
compounds by infrared methods. When used with other physical
measurements, the infrared method aids inorganic analysis. There
are numerous reviews [9 ' 10 ] in the Iiterature with regard to quan-
titative analysis of organic compounds. These are also pertinent
for inorganic compounds since the same principles hold in both cases.
Miller and Wilkins [8 ] reported the spectra of numerous inor-
ganic compounds. I t is apparent from their work that a number of
discrete absorption regions exist which are characteristic of the type
of anion present. Qualitative identification of various inorganic an-
ions can be made from their correlations. Similar correlations have
since been made for various other inorganic compounds, and these
can aid in making qualitative identifications. Several examples of
quantitative infrared analyses have been reported. Hunt el al. [u· 12 ]
analyzed a number of rocks and minerals. Corbridge [13 ] has clone
some quantitative work on condensed phosphates.

INFRAREDSPECTROSCOPY
OF COMPLEX INORGANIC MOLECULES
Applications to Structure Determination
of Complex lnorganic Molecules
Infrared spectroscopy has assisted in the determination of the
structure of certain complex inorganic molecules, such as the meta]
carbonyls, inter-halogen compounds, boron hydrides, and nitrogen
oxides. The practice used has been to compare the observed spec-
trum with the spectrum expected for an assumed model on the basis
lntroduction to lnorganic Infrared Spectroscopy 37

of group-theory-derived selection rules. The dependability of this


procedure depends on the degree of reliability of the observed spec-
trum. I t is very dangerous to use this method if the observed spec-
trum is poorly resolved. In addition, failure to observe as Ihany
bands as are required by the selection rules is no basis for rejecting
a certain model. The metallic carbonyls illustrate this point very
weil.
Metallic Carbonyls. Sheline [14 - 16 ] has examined the infrared
spectra of the iron carbonyls Fe2(C0)9, Fea(C0)12, and Fe(CO)s.
The carbonyls of cobalt [17 ' 18 ], Co2(CO)s and Co4(C0)12, have also
been studied. X-ray diffraction data [19 ] have indicated that in some
of these carbonyls there are two kinds of carbonyl groups: the "bridg-
ing" type and the "end" type. Infrared data for some of these com-
pounds have shown absorption in the 2000 cm - 1 region, and this
has been attributed to the "end" carbonyls. Another absorptionwas
found in the 1800 cm- 1 region; this was attributed to the "bridged"
carbonyl group.
The assignment of the band in the 1800 cm - 1 region to a bridged
carbonyl group can be confirmed by chemical methods [20 1. Two
bridging groups can be replaced by one molecule of acetylene and
the 1800 cm - 1 band disappears.
lron enneacarbonyl, Fe2(C0)9, was found to have C-0 Stretch-
ing frequencies at 2080 and 2034 cm - 1 due to the terminal carbonyl
groups, and an absorption at 1828 cm - 1 due to the bridged group
[161 The structure proposed for this compound was that shown in
Fig. 1.
Diffraction data for iron tetracarbonyl, Fea(C0h2, arenot avail-
able. Infrared studies [15 ] showed bands at 2020, 2043, and 1833

Fig. l. Proposed structure for Fe,(CO) •.


38 John R. Ferraro

Fig. 2. Proposed structure for


Fea(CO)u.

cm - 1 and the proposed structure is shown in Fig. 2. Cotton [15 ] has


found an additional band at 1997 cm- \ using LiF optics, which
indicates that Sheline's structure is incorrect. The proof of this struc-
ture is still open to discussion.
The recent work of Cotton and Monchamp [21 ] in regard to the
carbonyls of cobalt-Co2(CO)s and Co.(C0)12- is of particular im-
portance. Original work with Co2(CO)s had shown bands at 2034,
2054, 2077, and 1858 cm - 1; from this it was inferred that both "end"
and "bridging" carbonyls existed in the rnolecule, and the struc-
ture proposed (Fig. 3) was that of two trigonal bipyramids joined
r.t an edge [17 ' 181 Using calciurn fluoride optics, Cotton et al. [21 ] found
bands at 2075, 2064, 2047, 2035, 2028, 1867, and 1859 cm- 1. The
0 0
I o I
c c~ c
O::aC-co1/~1co-ca.o
l~c~lc
c 0 -? Fig. 3. Proposed structure for
R I Co.(CO)s. D.. symmetry-
0 0 trigonal bipyramid [17 l.
Introduction to lnorganic Infrared Spectroscopy 39

?,8
\I c,O

/o~c~Co(C0>
kc,;,' ~
2 Fig. 4. Structure of Co.(CO)"
(CO)
2
Co~
~\~,
\"c-o according to Carradini and
~--Co(C0) 2
Ercoli [22 ].
0

appearance of five terminal fundamental frequencies and two bridg-


ing bands ruled out all of the previously proposed structures. In a
similar fashion, the structure proposed for Co4(COh2 was found to
be in error [21 1 The new structure proposed has been substantiated
by x-ray studies (Fig. 4) [ 22 1
The manganese and rhenium compounds-M2(C0)10-do not
possess bands in the 1800 to 1900 cm - 1 region and are believed,
as a result, not to contain a bridged structure [23 1 X-ray diffrac-
tion data have recently confirmed this [24 1 The structure proposed
is that of the octahedrons joined by the M-M atoms and at 45°
to each other.
The interpretation of the structures of the simpler carbonyls
was also aided by infrared spectroscopy. Chromium, molybdenum,
and tungsten form hexacarbonyls of the type M( CO)s. Electron-
diffraction and x-ray studies have indicated a regular octahedral
structure [25 ' 26 ]. Infrared measurements have confirmed this.
The infrared spectrum of Fe(CO)s has shown that the com-
pound has a trigonal bipyramid structure [161 The assignment of
the observed frequencies of the gas was successfully made on the
basis of a trigonal bipyramid model (Fig. 5). Recently [27 ] the stereo-
chemistry of five-coordinate compounds of type LFe(CO). or
L 2Fe(C0) 3, where L is PhaP, MeNC, EtNC, PhNC, BuNC, or
(PhNC) 5Coi+ has been examined. By means of the infrared spectra
and comparison with the selection rules, the configurations were

Fig. 5. Proposed structure for Fe(CO)..


40 John R. Ferraro

concluded to be very probably as in Fe(CO)s, trigonal bipyramids.


Interhalogen Compounds. Several of these compounds have
been investigated by the infrared method and their structures elu-
cidated. The compound IFs illustrates how Raman and infrared
spectra can together aid in structure determination. The Raman
spectrum of the liquid [28 ] and the infrared spectrum of the gas [28 ]
were measured. Lord et al. compared their observations with the
predicted number of frequencies for seven possible symmetries for
the molecule (Table I).
Structures 5, 6, and 7 are immediately eliminated, as are struc-
tures 1 and 2. Thus, the structure of IFs is either 3 or 4 (4 being a
tetragonal pyramid), providing the spectrum is highly resolved. In
a similar way the structure of IF 7 was postulated to be a pentagonal
bipyramid.
Boron Hydrides. Infrared examination of diborane (B2H 6 )
showed that it had eight bands, which appear to be fundamentals
[29 ]. If the structure is of a bridge type,

then the selection rules predict eight infrared vibrations. Alumihum


borohydride, AI(BH4h was also investigated by infrared and re-
sults [30 ] were interpreted on the basis that the structure has hy-
drogen bridges as in diborane.
Oxides of Nitrogen. The establishment of structures for the
various oxides of nitrogen has also been helperl by infrared measure-
ments. Nitrous oxide was shown to be unsymmetrical and linear
[31- 33]
+ .. .. .+ +
:N =N =O:~N=N =0~ :N-N=O:
Nitrogen tetroxide has been studied in the solid, the liquid, and the
vapor state and has led Sutherland [34 ] to predict a planar structure.
Recent confirmation of this was made by Snyder and Hisatsine
[ 36 ]. Nitrogen pentoxide was shown to have the structure

0~ /"0
~N-0-N~
0~ ~0

in the liquid state [36 ].


lntroduction to lnorganic Infrared Spectroscopy 41

TABLEI
Application ofthe Vibrational Selection Rules
to tbe Possible Structure of IF5

Point Total Roman spectrum Infrared Coincidence


Structure
group frequencies Total Polarized spectrum Total Polarized

o•• 7 3 3 0 0
2 o•• 8 6 2 5 3 0
3 c,, 7 7 2 4 4 2
4 c., 9 9 3 6 6 3
5 Ca, 8 8 4 8 8 4
6 c,, 12 12 5 11 11 5
7 c. 12 12 8 12 12 8
Observed 9 8 3 4 3 2

INFRARED SPECTRA OF COORDINATION COMPOUNDS

Infrared spectroscopy has been a very useful tool in the field


of coordination chemistry. It has aided in the problems of struc-
ture determination, cis-lrans isomerism, metal-ligand site attach-
ment, and in determining bond types in these complex molecules.
Only several examples in which the infrared spectra of coordination·
compounds has been instrumental in solving the aforementioned
problemswill be presented. Numerous others are known and may be
found in the literature. A large effort in this field has been made
at N otre Dame by Quagliano and Mizushima.

Structural lsomerism
The structural isomerism arising in the complex ions nitropen-
tamminecobalt (111), [Co(NHa).N02)2+, and nitritopentammineco-
balt (111), [Co(NHa).ONOJ2+, has been reported (see Table II). From
analogy with the colors of compounds known to possess M-0 or
M-N links, the stable yellow-brown form was considered to have
the Co-N link, while the unstable red form was considered to have
a Co-0 link. The verification of these postulates has now been ac-
complished by infrared techniques [37 ]. This was clone by observing
the growth of peaks at 1430, 1315, and 825 cm- 1 , with a decrease
initially in intensities of the absorptions at 1460 and 1065 cm- 1 as
freshly prepared red [Co(NHa) 50NO]Cb aged. Eventually the peaks
at 1460 and 1065 cm- 1 disappeared and the spectrum became that of
the yellow-brown [Co(NHa).N02]Cb.
42 John R. Ferraro

TABLEU
Differences in Infrared Absorption of tbe Ions
[Co(NHa)sN02]2+ and [Co(NHa)sONOf+

-I
Ion cm Assignment

( Co(NHa)•NO.J" + 1430 N02 (st.) ontisym.


1315 N02 (st.) sym.,
ond NHa def. sym.
825 N02 (def.)
1460 0-N-0 (st.) ontisym.
1065 Q-N-0 (st.) sym.

Site of Attachment of Metal to Ligand


Infrared spectroscopy has proved helpful in determining the
site of attachment of the meta) to the Iigand.
The thiocyanate ion is bifunctional and can be attached to a
metal in three ways, M-S-CN, M-SCN-M, and M-NCS. The
case where the thiocyanate acts as a bridge is discussed later. A
whole series of compounds have been studied by infrared to deter-
mine whether the meta} is attached to the sulfur or the nitrogen
atoms. The latest investigation [38 ] has centered on the C-S stretch-
ing vibration. Wherever the bonding is to the sulfur atom, the C-S
frequency is found in the range 690-720 cm - 1 • If the bonding is
to the nitrogen atom, the C-S frequency is found in the range
780-860 cm - 1•
In the coordination compounds involving urea and thiourea as
ligands [39 ], the problern involved is whether one has a metal-nitro-
gen bond or a metal-oxygen bond, in the case of urea. The infrared
spectra of these complexes showed that urea formed metal-nitrogen
bonds with Pt (II) and Pd (II), and metal-oxygen bonds with
Cr (111), Fe (II I), Zn (II), and Cu (II). These conclusions were
reached by a comparison of the spectra of the complexes with that
of free urea. lf the coordination involves metal-oxygen bonds, the
spectrum would be expected to differ only slightly from that of
urea. The C=O absorption would shift toward lower frequency [the
C=O absorption region at 1700 cm- 1 is blank in the Cr(lll), Fe
(111), Zn (II), and Cu (II) compounds, while in free urea it is at
1683 cm- 11 If metal-nitrogen bonds are involved, then the spectrum
is significantly different from that of the free urea molecule. The
NH stretching, NH deformation, and CN vibrations would be ex-
lntroduction to lnorganic Infrared Spectroscopy 43

pected to shift toward lower frequencies, as indeed they do in the


Pt (II) and Pd (II) compounds. In addition, the absorption due to
the carbonyl group is shifted to 1720 cm - 1 because of the blocking
of resonance between the bonded nitrogen and the C=O group, as
one would expect.
Similar comparisons of the spectra of the metal-thiourea com-
plexes with that of free thiourea showed that all metal bonds were
to sulfur [40 ]. The spectra were all similar to the spectrum of
thiourea, with the exception that the C=S frequency was shifted
to lower values.

Cis-Trans lsomerism
Infrared spectroscopy has aided in distinguishing between cis
and irans isomerism in inorganic coordinated compounds. For ex-
ample, cis- and lrans-dinitrotetraammine cobalt (111) chloride,
[Co(NHa)4(N02)2]Cl, can readily be distinguished by their spectra
[41 ]. Fewer absorption peaks were present in the irans compound
than in the cis. This can be a direct consequence of the selection
rules since the lrans complex has a center of symmetry while the
cis complex does not; therefore, the lrans compound might be ex-
pected to give a less rich spectrum. However, only one example
was given. I t would be of interest to discover if other cis-lrans iso-
mers give the same results.
An excellent review on the "Infrared Spectra of Transitional
Metal Complexes" by F. A. Cotton has recently appeared in Modern
Coordinaiion Chemislry by J. Lewis and R. G. Wilkins. *

INFRARED SPECTRA
OF VARIOUS ORGANOMETALLIC COMPOUNDS
Salts of Carboxylic Acids
The salts of the carboxylic acids have been extensively studied
by Lecompte [42 - 45 ]. When dealing with salts of acids the charac-
teristic carbonyl absorption is lost and is replaced by two bands
between 1550 and 1610 cm- 1 corresponding to the antisymmetrical
and symmetrical vibrations of the COO- group.
In the solid state the two frequencies vary with the nature of
the metallic ion. For mono- and divalent elements there is a linear
relationship between the electronegativity of the element and the
*lnterscience Publishers, lnc., New York, 1960.
44 John R. Ferraro

asymmetric stretching frequency [461 Stimson [47 ] has also noted


similar dependencies in salts of substituted benzoic acids.

Salts of Phosphorus Oxy-Acids


The spectra of a number of inorganic salts of the phosphorus
oxy-acids were measured in the NaCI region [13 ' 481 The absorptions
of each type of anion were characteristic, and correlations were sug-
gested for various structural groupings in these substances. The
hydrated salts all absorb in the OH region of water at 3300 and
1640 cm - 1 • In addition, the spectra are rieb in the region 900-1400
cm- 1 , and these are attributed to P-0 associated vibrations (e.g.,
P=O stretching, ionic Poo-, P0a 2 - and P-0-P).

Metal Complexes of Acetylacetone


A number of meta] complexes of acetylacetone have been pre-
pared and studied by infrared methods [49 - 561 The infrared results
with acetylacetone are consistent with a conjugated chelate struc-
ture resonating between forms I and II. It would be expected that
coordination to-a meta] (111) would shift the carbonyl frequency to
lower values and shift the C-H stretching absorption to higher fre-
quency (new environment more like benzene ring); the antisymmetric
and symmetric methyl stretching vibrations should remain about
where they are in acetylacetone and the OH ... 0 absorption should
disappear. All of these expectations have been realized in theinfrared
spectra of these compounds. Efforts to correlate the shift of the car-
bonyl frequency with the strength of the complex have been also
made [55, 56].

II
lntroduction to lnorganic Infrared Spectroscopy 45

M
/~
0 0
II I
/c _-:?c
HaC
'~"
H
C CHa

III

INFRARED SPECTRA
OF ACIOIC PHOSPHORUS COMPOUNDS
The industrial uses of phosphorus compounds in recent years
has grown rapidly. Phosphorus compounds are used in food manu-
facture and water treatment, as additives in the oil industry, and
as detergents, insecticides, and solvent extractants (ore processing).
It is in the field of solvent extraction that many of the organo-
phosphorus compounds have made valuable contributions of late.
The infrared study of these compounds was started by Daasch
and Smith [57 1 They published spectra of 60 organophosphorus de-
rivatives and proposed spectra-structure correlations. Bellamy and
Beecher [58 ] extended these studies, as did others [48 ' 59 - 66 ]. Most
of this work was done on the neutral type of esters. The acidic type
of esters has gained more attention in the past five years, with the
groups at Argonne, Oak Ridge, and Harwell laboratories evaluating
these acids as solvent extractants for various cations. In the course
of this work many new acidic-type organophosphorus compounds
have been synthesized and subjected to infrared sturlies [67 1
The infrared sturlies of the acidic type of organophosphorus
esters of the type (GOhPOOH, G'OGPOOH* have been reported
[ 67 1 These acids have been found to be dimeric in most solvents

and intermolecular hydrogen bonding has been postulated. Despite


the fact that these compounds are quite complex, the infrared spec-
tra can be qualitatively analyzed in terms of vibrations involving
the phosphorus atom and those involving the G group. The spectra
are characterized by broad regions of absorption at about 2500-
2700 cm - 1 and about 2300-2350 cm - 1 [ 67 ' 68 ], and these have been
attributed to the bonded P-OH stretching motion [57 ' 58 ]. In ad-
*G can be alkyl, aryl, or variant thereof.
46 John R. Ferraro

dition, a third broad region appears at about 1680 cm- 1, which is


attributed to the bonded P-OH deformation motion [69 ' 70 ]. These
regions all disappear on salt or metal complex formation, and are
appropriately shifted to lower frequencies on deuteration. The P---.0
stretching vibration is very strong and is observed in the 1200 cm - 1
region. The identification of this absorption is aided by salt or com-
plex formation. The strongest absorption appears in the 1000 cm- 1
region and is probably due to several vibrations, P-0-(G) and
(P)-0-G. When Gis aryl, the P-0-(G) vibration (asymmetric)
appears at about 966-1010 cm- 1 [ 64 1 When Gis alkyl, it is found at
about 1000-1050 cm - 1 • In aryl phosphorus acids the vibration at 1180
cm- 1 is attributed to the (P)-0-aryl stretching motion. The vari-
ous CH vibrations are located in the expected positions of the spec-
tra (CH stretching, 2800-3100 cm- 1 ; CH deformation, 1380-1480
cm- 1 ; C=C skeletals in the aryl ring, 1590-1610 cm- 1 and 1500-
1a18 cm -I; CH out-of-plane vibrations in aryl phosphorus acids,
700-835 cm - 1 ).

INFRARED APPLICATIONS IN DIFFERENTIATING


BETWEEN AN IONIC BOND AND A COV ALENT BOND
IN COMPLEX COMPOUNDS
The use of infrared spectroscopy in differentiating between an
ionic bond and a covalent bond in a complex (in the Iigand-metal
bond) where the Iigand is nitrate, carbonate, sulfate, iodate, thio-
cyanate, or cyanide has been reported. The method has been par-
ticularly useful in the case of nitrates, carbonates, sulfates, and
iodates while not so successful in the case of thiocyanates and cy-
anides.

Nitrates
The nitrate ion is considered to have the configuration of an
equilateral triangle possessing the point group Dah symmetry. In ni-
trate compounds in which the nitrate is covalently bound the sym-
metry lowers and is changed to that of a point group C2v symmetry
[I]. Thus, in going from a Dah symmetry to one of C2v, the Pa fre-
quency in the symmetrical N03 ion (point group Dah) undergoes
splitting into two new frequencies. One component is observed to
shift toward higher frequency (P4) at about 1500 cm-I, and the other
toward lower frequency (PI) at about 1275 cm -t, both of point group
lntroduction to lnorganic Infrared Spectroscopy 47

C2v symmetry. In addition, 112 appears at about 1000 cm-\ as does


the 1'6 frequency at about 800 cm - 1.
Gatehouse [72' 73 ] and Quagliano [74• 75 ] have recently examined
the infrared spectra of several nitrato complexes of the transition
elements, and have observed tbe changes in symmetry occurring
when the nitrate is in and out of the coordination sphere of the
cation. They have been able to distinguish between the nitrate ion
and a covalently bonded nitrate group in these compounds. Addison
and Gatehouse [76' 77 ] have also examined several anhydrous nitrates
in this way.
Peppard and Ferraro [78 ] have applied this method to the study
of the organophosphorus complexes of nitrates. They have examined
theinfrared spectra of the nitrate-bis-(2-ethylhexyl) phosphate com-
plexes of M (IV) cations, and have noted the lowered symmetry in
these complexes. Ferraro [79 ] studied the nature of nitrate in the
TBP ( tri-n-butyl phosphate) solvated nitrates [M (111), M (IV), and
M02 (II) type] and observed a greater lowering in nitrate symmetry
in these complexes than is present in the hydrated nitrates them-
selves. The nature of the mineral acid (HN03) extracted into
HDEHP [bis-(2-ethylhexyl) phosphoric acid] and TBP was also stud-
ied by this method [801
The infrared spectra of several metallic nitrates were examined
[81 ] and the observation was made that in going from a monovalent
metallic nilrate to a tetravalent metallic nilrate there is an increased
lowering of the nitrate symmetry, and a transition from a point
group D3h symmetry to a point group C2v symmetry.
The observed changes in the nitrate symmetry in inorganic
nitrate compounds have proved to be very useful in giving additional
information as to the nature of the nitrate present.

Carbonates
As with the nitrates, Gatehouse el al. [82 ] h'ave attributed the
decrease in symmetry arising in carbonates to covalent bonding.
The carbonate ion has a D3h symmetry giving rise to four vibrations.
When the carbonate ion is covalently bound through one or two
oxygens, the symmetry is lowered to that of point group C2v· The
113 vibration in the carbonate ion is in a doubly degenerate state
and is split into two components, "• and v~, when the carbonate ion
is coordinated. The compounds listed in Table Ill illustrate the re-
sults obtained for a covalent carbonate. The basic carbonates and
hydrogen carbonates also show this splitting: Table IV illustrates
the frequency range of the carbonate absorption bands.
48 John R. Ferraro

TADLE 111

Compound v. VI V2 V8 va or Ps

[Co en COalcl 15ns 1281s 1059w 830s 754m


1272s 1035w
Dimethyl
carbonate 1760s 1280s 969s 793s

TADLE IV
Frequency Ranges of Carbonate Absorption Bands, cm _,

Type of
va
carbonate

Simple 1470-1420 1090-1020 890-820 750-680

OH v. ., V2 V6 va or vs

Ba sie
Camplex
3390-3270
1577-1493 1338-1260 r
1515-1470 1425-1325 1049-1047 877-835
082-1 055 889-824
1050-1021
712-686
809-738

Acid 3300-3200 f660-1655 f410-1400 f050-1010 840-830 705-688


1630-1620 1370-1295 1000-990
Orgonic 1870-1750 1280-1252 1021-969 793-774

Sulfates
The So~- ion has a Td symmetry [71 ] with four fundamentals
allowed in theinfrared spectrum: v 1 at 981 cm- 1, v 2 at 451 cm-\
va at 1104 cm- \ and v. at 613 cm - 1 • The va and v4 frequencies are
triply degenerate and upon coordination to a metal atom lose their
degeneracy and split into several frequencies. The frequency va at
1104 cm - I in so!-
ion splits into four bands at 1278, 1137, 1045, and
975 cm - I when it becomes coordinated to cobalt, e.g.,
[Co( NHa) 5SO.]Cl [75 ' 83 ].

Iodates
The iodate ion possesses a pyramidal configuration (point group
C3.) and four fundamentals are allowed and observed in the infra-
lntroduction to Inorganic Infrared Spectroscopy 49

red spectrum: 111 at 779 cm - 1 , 112 at 390 cm - 1 , 113 at 826 cm - 1 , and


114 at 330 cm - 1 [ 84 1 The 113 and 114 fundamentals are doubly degenerate

and upon coordination to a metal atom will split. The symmetry


is lowered to a C. type and the number of infrared active funda-
mentals is increased to six. Dasent and Waddington [85 ] have re-
ported on the infrared spectra of several simple and complex iodates
in which the results have been interpreted in terms of an -O-I0 2
group bonded covalently to a metal atom.

INFRARED SPECTRA OF BRIDGED INORGANIC ANIONS

Another area where infrared spectroscopy has proved invaluable


has been in establishing the existence of bridging groups such as
CO, SCN, and N02 in metal coordination complexes. The metallic
carbonyls, which have bridging CO groups, have already been dis-
cussed. .

Thiocyanates
Chatt and Duncanson [86 ] have determined the infrared spec-
tra of several thiocyanato complexes of platinum (II) and of pal-
ladium (II). All of the monomolecular complexes-e.g., L2Pd(SCNh-
have an absorption in the 2100 to 2120 cm- 1 range. The bimo-
lecular complexes-e.g., L2Pd2(SCN)2Cb-have an absorption in the
2150 to 2182 cm- 1 range. These results led Chatt and Duncanson
to the conclusion that bridging thiocyanates are present in the bi-
molecular complexes.

Nitro Compounds
In compounds of the type L2Pt(N02h with terminal nitro groups
absorption occurs at 1390-1440 cm - 1 (asymmetric N02 stretching vi-
bration), and 1318-1340 cm- 1 (symmetric N02 stretching vibration).
In compounds with bridging nitro groups absorption occurs in the
1470 to 1485 cm - 1 region and in the 1200 cm - 1 region, and the
bands are broader and somewhat less extensive than those for ter-
minal N 02 absorption [87 ].

FAR-INFRARED SPECTRA OF INORGANIC COMPOUNDS


A recent publication [88 ] reported on the infrared spectra of
over 200 inorganic compounds in the cesium bromide region. Char-
acteristic frequencies are listed for inorganic ions in the 300 to 700
50 John R. Ferraro

cm - 1 region, together with the assignments made for these frequen-


cies.

THEINFRAREDSPECTRA
OF METAL-OXYGEN DOUBLE BONDS

The infrared spectra of several compounds containing metal-


oxygen double bonds has been reported [89]. The results show that
in compounds where one metal-oxygen double-bonded link exists,
an absorption occurs at 952-1087 cm- 1 • The compounds studied in
this dass were VOSO., VO(acetylacetone), Ti(acetylacetoneh,
K2MoOCls, K2CrOCls, and VOCb. In compounds where two oxy-
gens are linked to the metal (e.g., Cr02Cb, Cr02F2), the absorption
occurs at 970-1016 cm- 1 • In compounds where there are more than
two metal-oxygen bonds (V 2Üs, CrOa, MoOs, KMnO., KReO.,
K2CrO., K2Cr207), the absorption occurs at 825-1020 cm- 1 • The ab-
sorptions in this region are of diagnostic value if no atom of simi-
lar atomic weight is present which might give frequencies in the
same region.

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