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Infrared Spectroscopy*
John R. Ferraro
Argonne National Laboratory
Argonne, Illinois
*Based on work per.fonned under the auspices of the U.S. Atomic Energy Commission.
35
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.
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
?,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
0~ /"0
~N-0-N~
0~ ~0
TABLEI
Application ofthe Vibrational Selection Rules
to tbe Possible Structure of IF5
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
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
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
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
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
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
TADLE IV
Frequency Ranges of Carbonate Absorption Bands, cm _,
Type of
va
carbonate
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
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
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 ].
THEINFRAREDSPECTRA
OF METAL-OXYGEN DOUBLE BONDS
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