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INFRA-RED ADSORPTION SPECTRA OF METALLIC

ACETYL -ACETONATES

BY JEAN LECOMTE
Received (in French) 20th July, 1950
The absorption spectra of seven metallic acetyl-acetonates have been obtained
from the powders in the region 525-1750cm.-l. These experimental results
are interpreted in terms of the vibrations of the carbon chain and the CH2 or
CH, groups, and taking account of the keto-enol isomerism. The changes
caused in the spectra by the presence of the metal are stressed. From the
infra-red spectra it is deduced that the acetyl-acetonates behave as complexes
and that a cyclic formula is most probable.

The work * was commenced in 1g3g.l but it did not give any clear
interpretation of the spectra of the three metallic acetpl-acetonates studied,
and we have since repeated this work and increased the number of sub-
stances studied to seven, using instruments built by Perkin-Elmer and
Beckman in the region 700-1750 cm.-l (cf. spectrograph of weak dispersion
used during 1939 and 1940). We have extended the range between 525 and
700cm.-l by using a prism of sylvine in the spectrograph. The spectra
were easily obtained with dry powder using either the technique previously
employed a t the Sorbonne,2 or by moistening the powder with Nujol.
We have also examined the spectra of freshly distilled acetyl-acetone.
Four metal acetyl-acetonates were studied in the same way as Morgan 3
with acetyl-acetone between 400 and 3000 cm.-l, mainly with the object
of investigating the characteristic bands of the metaI-oxygen bands.
I n the interpretation of our measurements we use these results in the same
way as those obtained for the Raman effect by Kohlrausch and his col-
laborators* on the important series of substances showing keto-enol iso-
merism.
Experimenta1 Results
Our results are summarized in Fig. I in which the positions of the absorption
bands are indicated by lines, the height of which is proportional t o the intensity.
This Figure also includes Morgan’s results. On the whole we find the same
behaviour as that found by Morgan, but our results for ferric acetyl-acetonate
do not agree with his. (This is the only acetyl-acetonate which is common to
both sets of results.) We consider that this difference is due to the fact that
the preparations did not lead t o the same product in both cases.
From Morgan’s results for the region 400 to 525 cm.-l and from our results
for the region 525 t o 1750 cm.-1, the main regions of absorption for all the acetyl-
acetonates are found in the same position, whatever the metal, and have mean
wave numbers as follows :
410 450 and 470 512 and 530 760to 824 930 1020
F 2 3 4 5 6
1185and 1266 1310t o 1368 1400 1450 1520 1560 cm.-l.
7 8 9 I0 I1 I2

* Carried out in collaboration with M. Rend Freymann, Professeur A la Facultd

des Sciences de Rennes. and with M. Clement Duval, Maftre de Recherches au
Centre National de la Recherche Scientifique
Lecomte and Freymann, Compt. rend., 1939,208,1401.
Lecomte, Cahiers physique, 1943,17,I.
Morgan, U.S. Atomic Commission, 1949 ; AECD, 12659, 16.
Kohlrausch and Pongratz, Ber., 1934,67, 976, 1465 ; Kahovec and Kohl-
rausch, Ber., 1940,73, 1304 ; Kohlrausch and Pongratz, Sitz. Akad. Wiss. Wien.,
1937, 146, 226 ; Monatsh., 1937,70, 226.
125
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I 26 h1 ETA1,L IC AC E'TY L-AC ETONA'I'ES

A certain number of well-defined absorption maxima also exist between 600
and 700 cm.-l t o which we refer later.
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Interpretation of Results .-An interpretation of the vibration spectra

of metallic acetyl-acetonates does not seem t o have been previously attempted
and an approach has only been made t o certain parts of this difficult problem.
For the sake of clarity we use a, semi-empirical method in considering in turn :
(i) the bands due t o skeletal carbon atoms (and also the hydrogen atoms), but
not of the metal, nor of the keto-enol isomerism ; (ii) the bands due to keto-enol
isomerism ; (iii) the bands due to the presence of metal.
When we consider the problem of the whole system it appears too difficult t o
solve by methods a t present available, using the number of relatively important
vibrating masses, and also the influence exerted by the metal on the spectra
about which so little is known, for compounds such as acetyl-acetonates.
Although the method appears to be somewhat indirect and is open to criticism,
we shall, where possible, consider the problem to be one analogous to that of
a carbon chain of the acetyl-acetone type, with w b c h in fact we are left after
removal of the metal. Then we investigate how the metal interferes, and con-
sider possible new structures. We assume that although the final structure

400 500 600 700 BOO 900 I000 IJOO /ZOO f300 /400 /500cm-'
I 1 4 0 '

Be < '
I ,

co +++
I

1I

cu I
I

I I I#
J
ill,
I
I ,

, I I I" 'I
,, i I
FIG I.

may be cyclic, we apply conclusions obtained from the consideration of a non-

cyclic type. In effect, the cyclic form is necessary to explain our results, but
such a specialized cyclic structure need not be considered as a whole, as we do
for aromatic and cyclohexanol nuclei (at least for the modes of vibration of
the carbon chain). On examining the cyclic structure in its several parts, the
constitution of which need only be known to a first approximation, we are able
to obtain interpretations which are clearer than those obtained from the study
of the problem as a whole.

Discussion
1.-Bands Due to Skeletal Carbon Atoms or CH2 or CH3 Groups.-
( a ) To simplify the problem we consider the carbon chain of acetyl-acetone
in the keto form in which the groups CH, and CH, appear as single entities
(it may be noted that if the ion is in the enolic form, with the groups
CH, CH, and OH considered as points, the result is the same). With the
molecular model for seven masses similarly constituted the number of
fundamental vibrations is 15. It is interesting t o note that modes of
vibration are obtained which, as a first approximation, are applicable to
the acetyl-acetonat es.
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JEAN 1,ECOMlE 127

U’e note that it is possible to consider the carbon skeleton of acetyl-
acetone as formed by the combination of two molecules of acetone con-
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nected by a common CH, group, thus :

0 0 0

acetone acetyl-acetone.
The modes of vibration of a molecular model are then obtained in the form
of a coupled double Y structure sometime in-phase and sometime out-of-
phase, i.e. the six well-known modes of vibration for acetone considered
as a model in the form of a Y structure with the C€13 groups as points.
This leads to 1 2 modes of vibration to which must be added 3 others
obtained by appropriate coupling of one translation and two rotations
which do not give absorption bands for the free acetone molecule. One
thus gets the scheme shown in Fig. 2. Two of these modes of vibration

A A A
u u ’ ~

+LA Y: - i u
v9 +

FIG.2.

are inactive in absorption. The symmetry of the scheme conforms to

that found for a molecular model of symmetry‘ CZvwith one mass vibrating
on the binary’ axis and three symmetrical masses on both sides of the
axis.
Our procedure gives a ready interpretation of the absorption maxima
of metallic acetyl-acetonates as being due t o the skeletal carbon atoms.
In effect, the coupling of a single vibration of acetone, sometime in phase
sometime out-of-phase, produces two vibrations of acetyl-acetonates the
wave numbers of which have a small separation and which also approach
the vibrations of acetone by which they are caused. The maxima in-
cluded in the regions I, 2 , 3, 4 and 7 can be compared with the following
vibrations of acetone.
w3 w5 Wl WP
390 (D) 489 (P) 527 (D) 787 (P) 1225 (D) cm.-I.
The letters D and P indicate polarized or depolarized Raman lines.
We consider further the vibration w,. It will be difficult to claim a
better agreement between the calculations and the spectra of the acetyl-
acetonates. It may be noted in passing that region I only gives a single
band for these latter substances because coupling in-phase and out-of-phase
of the w 6 vibration of acetone leads only to an active vibration in the
infra-red for the simplified model considered here.
(b) I f we now take into account the characteristic vibrations of the
CH, and CH, groups, we find a new series of bands which can also he
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128 METALLIC ACETYL ACETONATES

compared with those of acetone. We have previously given an analysis
of the vibrational spectra of the latter substance. But here we must note
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that the coupling in-phase and out-of-phase of two molecules of acetone

will probably not produce large differences between the wave numbers
with the result that the bands will be considered as single ones for the
acetyl-acetonates as is confirmed by experiment. The agreement found
with the older measurements on acetone is given as follows :
Acetone . * (907 918) 1070 1060 (12981346) (14291444)cm.-l
Ra IR IR Ra IR Ra IR Ra
Acetyl acetonates 920-930 1005-1025 ? 1310-1368 1447-1460cm.-l
11.-Bonds due to Keto-enol Isomerism.-The question of the keto-
enol isomerism is more complicated than the preceding one because the
molecular structure is not exactly known and because, a t least in the
enolic form, the position of the bands usually attributed to C=C and
C=O undergo important variations.
Our measurements lead to the conclusions that metallic acetyl-
acetonates, exist solely in the enolic form and that a cyclic formula of
the Sidgwick type best represents the experimental results.
We will now give a brief review of the wave numbers attributable t o
the vibrations of the CO bond. These results then help in the interpretation
of the metallic acetyl-acetonate spectra and allow a choice between the
possible enolic structures.
(a) We recall the well-known result that the normal values of the
characteristic bands of the -0 group, for example those of the aldehydes
and the aliphatic acetones, as with the esters of formic acid, occur at about
1718cm.-1. The introduction of halogen atoms increases these wave
numbers appreciably. Numerous examples of the reduction of the fre-
quency are known in other work, for example, in aldehydes and aromatic
acetones, and recently Jones has given evidence showing that in the sterols
the CO band could be characterized by bands varying between quite wide
limits.
It is also noteworthy that in measurements made a t the Sorbonne on
almost a thousand salts of organic acids which ionize giving the carboxyl
group, a resonance was found to occur between the bonds of the carbon
atom and each of the two oxygen atoms. One can no longer speak of
0
a double or single bond, but one may write it in the form C 4 ,a grouping
O
\
in which the symmetrical and anti-symmetrical vibrations are a t 1300
t o 1400 and at about 1550 cm.-l. An analogous phenomenon seems
t o occur in substituted amides when resonance tends to reduce the bond-
ing force between carbon and oxygen and to increase that between
the bonding force between carbon and oxygen and to increa.se that between
carbon and the NH, group. We therefore write the formula

unsubstituted mono-substituted
amide amide
One can consequently determine from the vibration spectra whether a
CO group exists in a perturbed or unperturbed state, from the positions of
the characteristic bands between 1300 and 1750 cm.-1.
( b ) The above conclusions can be applied to the metallic acetyl-
acetonates. The complete absence of a band in the region 1700 to 1750
5Lecomte, J . Physique, 1945,6, 127.
6Lecomte, Rev. Optique, 1949,28, 353 ; Duval, Lecomte and Mme. DouvillC,
Ann. Physique, 1942, 17, 5 ; Mme. Douville, Duval and Lecomte, Bull. SOC.
chim., 1942,9, 548.
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JEAN LECOMTE
cm.-l shows that we are not dealing with a formula derived from the
ketonic form or acety'l-acetone.
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CH, CO CH, CO CH,.

The changes which we find in the characteristic frequencies of the CO
groupings favour the enolic form. The latter becomes more probable if
one considers the number of bands which occur in the region 1300 to 1600
cm.-l. We attribute two of these to the CH, or CH, groups (see above),
so that there remain three bands characteristic of the enolic form. These
latter are clearly interpreted in terms of an enolic form, two absorption
bands arising from the W , vibration of acetone (affected by the necessary
perturbations), and another Y,', from a translation mode of the acetone
molecule, but with the C==C bond perturbed.
One can then think of the strong bands between 1550 and 1562 cm.-l
on the one hand and between 1310and 1403 cm.-l on the other, as caused
by the two CO groups. Inasmuch as one can consider separately the bonds
between atoms without taking account of the rest of the molecule, the
first would represent a CO group with an attractive force reduced rela-
tively to a " double bond ; the second represents a single bond
" " "

of increased strength. In a paper on the esters of aliphatic organic acids

we have shown that this latter occurs in the region 1200 cm.-l.' (when we
are concerned with a simple non-perturbed bond). The variations of the
bonds between carbon and oxygen, which we have considered, apparently
tend to reduce the separation between the two wave numbers previously
indicated. In its turn the maximum found between 1500 and 1534 cm-.l
would represent a perturbed C=C bond.
We show that i t is equally possible to choose for the perturbed vibration
of C k C bond the intense band between 1550 and 1562 cm.-l and for the
perturbed C==O vibration, the band which exists between 1503 and 1534
cm.-1. We nevertheless think that the first alternative which we have
given above is the more correct by reason of the results of the Raman
spectra of zinc and aluminium complexes of acetyl-acetone, of methyl or
ethyl malonate (measured by Kohlrausch et d.).The study of analogous
compounds in the infra-red is in progress.
(c) Until now we have proceeded to the identification making use of
the maxima of the absorption spectra of various modes of vibration
without making a precise statement about the structure of the enolic
form and we were satisfied to indicate the changes in the normal character-
istic absorption bands of the different groupings caused by the presence
of the metal. The problem has been to indicate the nature of the vibrations
rather than to apply them to a known formula of the molecule. This
latter, however, will now be attempted. Kohlrausch, in particular from
a study of Raman spectra, has been interested in this question, and in the
case of acetyl-acetone has indicated the possibility of four enolic forms,
two mono-enolic and two di-enolic. We shall only reproduce the first two.
CH, - C(0H) = CH - CO - CH3,
CH, C(0H) - CH, CO - CH3,
2

and Kohlrausch shows that neither of these is satisfactory.

Limiting ourselves to the infra-red spectra, we observe that these
formulae indicate the existence of an OH group and that we will have to
find corresponding bands (fundamental and harmonics) in the near infra-
red which, however, are not found. Alternatively, the spectra would have
to be similar to those of the tertiary alcohols, but they actually show few
analogies to these. Also, in the region 10to 12 p one should find eT idence
of a double bond in the linear molecule, but the bonds of the acetyl
" "

acetonates do not correspond to what one would expect.

For these reasons, and others which have been given by other authors,

7 Lecomte, J . Physique, 1942, 3, 193.

E
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130 METALLIC ACETY L-ACETO NATES

a cyclic formula seems the most likely. With acetyl acetone the internal
cyclic formula explains perfectly why no OH bands exist (see the analogous
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classical cases of salicylaldehyde or of methyl salicylate).

With acetyl acetonates we have stressed that the introduction of a

metallic atom into the molecule leads to important changes in the positions
of the bands representing the C==O or C=C (perturbed) bonds. If the
metal is bonded to only one of the oxygen atoms the vibrations of the
two atoms is not markedly disturbed. We have shown, moreover, an
analogy between the acetyl-acetonates and the metallic salts of organic
acids in which we are concerned with the valency vibrations of CO. In a
number of different papers we have shown that even with monovalent
metals in the salts the metal is bonded t o two oxygen atoms in the ionized
carboxyl groups. We show below that it is not possible t o consider the
acetyl-acetonates as salts, but that the cyclic formula of Sidgwick is quite
satisfactory.
111.-Characteristic Bands of the Metal.-In the large number of salts
of organic and inorganic acids which have been studied a t the Sorbonne,
characteristic bands of the metal are not found. The latter appear then
as " transparent " in the region extending from the visible t o less than
500cm.-l (except for certain rare earth metals which show bands of an
electronic nature in the near infra-red). At most, one finds a few little
understood variations in the position of maximum absorption.
It is not possible with the few measurements available in the infra-red
to confirm the nature of the bonds between the metal and the oxygen
atoms according to the structure which we have indicated. It is, however,
certain that the metallic acetyl-acetonates do not behave as salts but as
complexes and in the same way we can forecast other physical properties.
At first the set of bands between 1310 and 1405 cm.-l and which we
have attributed to a CO vibration, were clearly displaced to the lower
frequencies according to the increase in weight of metal. We have never
found a similar result for salts.
The important point is that between 600 and 700 cm.-l, there are well-
defined bands the number and position of which vary with the metal.
The wave numbers which have been found are :
Be 661 (F) cm.-l.
Mg (after Morgan) 608 (F),621, 639, 642.
Cr 596 (F),606 (m), 650 (F),671 (F).
Fe+++ 660 (F).
Fe (after Morgan) 626 (F) 655.
c o+
f 666 (F).
co+++ 634 (F),669 (aF), 694 (F)
cu 607 (F),648 (F), 677 (aF).
Zn 622 (4,677 (4.
Th (after Morgan) 644 (F).
U (after Morgan) 619, 626, 651 (F).
I f the metal only plays an inactive role as in the salts we shall not
have to consider it when listing the vibrations. We have shown that all
the vibrations which were expected have been identified with sets of bands
which are found when one passes from one acetyl-acetonate to another.
To explain subsidiary absorption maxima between 600 and 700 cm.-l,
one must suppose that several molecular forms exist which have common
bands except in this region. This theory appears unlikely.
These difficulties are not present if one considers a ring in which the
metal is included. The list of vibrations shows that three are known,
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JEAN LECOMTE
besides that of the molecular forms in which the metal is not included.
In agreement with Morgan this argument leads t o the possibility of the
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bands in question being due to the metal-oxygen bonds. Unfortunately,

we have been unable to show the precise nature of these bonds so one can-
not state that they do not resemble those present in a salt. All that can
be stated is that the region 600-700cm.-~ corresponds to a relatively
feeble elastic force for these vibrations.
We have attempted to explain the variation in the position of Me-0
bonds, but have not reached any conclusive result. It may only be noted
that for the heavy metals, e.g. Th and U, the bands occur in the same region
as for light metals, e.g. Be. To a certain extent the atomic radius divided
by the valency of the metal helps in the elucidation of this fact.
It is not possible at present t o explain why the number of bands is
variable between 600 and 700 cm.-l as one passes from one metal t o another.
One would expect that associated with the metal one ring exists for mono-
valent metals, two rings for bivalent metals, etc. Unfortunately, as
indicated for example by Co++ and Co+++, the number of bands is not in
accord with the valency.
Conclusions.-In this work we have tried t o contribute to the know-
ledge of infra-red absorption spectra and to the analyses of the results
obtained. In elucidating the difficult problem of the structure of the
metallic acetyl-acetonates, we have accurately listed and identified the
vibrations of the carbon chain obtained with a structure which seems to
be cyclic (probably a single enolic form) and shown that complexes are
involved. Unfortunately a number of points remain unsettled, amongst
the most important being the manner in which the metal is bonded to
the rest of the molecule.
We hope to return t o this question in other work dealing with other
metallo-organic compounds which behave similarly to these complexes.

This work was carried out in the Laboratoire des Recherches physiques,
Sorbonne, under the direction of Monsieur le Professeur Cabannes to whom
we wish to express our sincere appreciation for the interest which he has
taken and for facilities placed at our disposal. Our appreciation is due
also to our colleagues M. Rent5 Freymann and M. Clkment Duval who have
allowed us access to unpublished work. Thanks are also due t o M.
Fauvarque and Mlle. Morandat for measuring and analyzing the spectra.

Laboratoire de Reserche physiques,

Sorbonne,
Paris.