Speotrochimica

Acta,19.53.
Vol.10,pp.307to 329. Pergamon
PressLtd.,London

The vibrational spectra and structure of ferrocene and ruthenocene

ELLIS R. LIPPINCOTT* and RICHARD D. NELsoNt$

(Received16 Nay 1957)

Ab&&--The infrared and Raman spectra of ferrocene, ferrocene-d-10 and ruthenocene are
reported. The observed spectra were found to be consistent with the D, model proposed for
the biscyclopentadienyl metal compounds. A detailed assignment of frequencies to the funda-
mental modes of vibration has been made for these compounds.
A normal co-ordinate analysis has been carried out using the vibrational assignment for a
ferrocene cyclopentadienyl ring. The similarity of the valence force symmetry constants
between benzene, tropylium ion and the cyclopentadienyl ring has confirmed the aromatic
nature of the C,H, ferrocene rings.

Introduction
PREVIOUS publications have given the tentative results of a spectroscopic study
of some metal cyclopentadienyl compounds [l, 21. The completion of the vibra-
tional analysis on Fe(C,H,),, Ru(C,H,), and Ni(C5H& has allowed an assignment
of frequencies to be made to the fundamental modes of vibration for these mole-
cules. The frequency assignment was facilitated and checked through the vibra-
tional analysis of Fe(C,D,),. We wish to present here a detailed explanation of
these frequency assignments as well as the results of a normal co-ordinate analysis
on a cyclopentadienyl ring of ferrocene.

Experimental
Ferrocene was prepared by the Grignard reaction described by KEALY and
PAUSON [3]. The product obtained was purified by repeated recrystallization
from ethyl alcohol followed by sublimation. Upon purification, orange-red crystals
were obtained which melted at 173-174°C.
Ruthenocene was prepared by the same procedure that was used for ferrocene.
However, in this case it was necessary to first prepare RuCI, as none was available.
The RuCl, was prepared by a procedure described in SID~WICK [4]. In this method
chlorine was passed over ruthenium powder heated to approximately 700°C in the
presence of carbon monoxide.
Purification of the ruthenocene product from the Grignard reaction by repeated
recrystallization from ethyl alcohol followed by sublimation yielded light yellow
crystals which melted at 196°C.
The method for the preparation of naphthalene-d-8 described by LIPPINCOTT
and O’REILLY [5] was slightly modified and used to prepare ferrocene-d-10.
Calcium oxide was prepared by the thermal decomposition of reagent grade
calcium carbonate. Ca(OD), was prepared by adding 99.8 per cent deuterium
* Department,of Chemistry, University of Maryland, College Perk, Maryland.
t Departmentof Chemistry,Kansas State College,Manhattan,Kansas.
$ A thesis presented as partial fulf?llment of the requirements for the degree of Doctor of Philosophy
in Chemistry at Kansas State College.

307
 ELLIS R. LIPPINCOTT and &CHARD D. NELSON

oxide to the calcium oxide. The exchange reaction was carried out in the following
manner. Five grams of Ca(OD), and 0.5 g of ferrocene were placed in a Carius
tube which was then evacuated and sealed. The tube was heated for 24 hr at
320°C in a Carius furnace. At the end of a run the ferrocene was removed from
the Ca(OD), by sublimation, placed with fresh Ca(OD), and the exchange reaction
rerun. After each run an infrared spectrum was taken to determine the degree
of exchange. As the deuterium content increased the intensity of the frequency
corresponding to CH stretching decreased. The low intensity of this frequency
was taken as an indication that the exchange was practically complete.
Added information on the deuterium content was gained through observation
of the infrared frequency corresponding to the anti-symmetric ring breathing
mode. This frequency occurs at 1108 cm-l in ferrocene and shifts to 1044 cm-l
in ferrocene-d-10. In partially exchanged ferrocene both of these frequencies
appear as well as several other frequencies which lie between 1108 and 1044 cm-l.
As the deuterium content increased the intensity of the frequency at 1044 cm-l
increased while the intensity of all the others decreased. The frequencies between
1105 and 1044 cm-l are thought to be due to cydopentadienyl rings containing
one, two, three and four deuterium atoms, respectively.
The sample on which the spectral analysis was made was estimated to have a
deuterium content 96 per cent of theoretical.
Infrared spectra were obtained by a Perkin-Elmer model 12-C single beam,
single pass, automatic recording spectrophotometer. The region 400-1200 cm-l
was studied with samples dissolved in Nujol using KBr optics. Spectra in the
region 1000-3500 cm-l were obtained in CS, and Ccl, solutions using NaCl optics.
The same instrument converted to double pass was used for the vapor spectra.
Vapor spectra were obtained through the use of a Perkin-Elmer model 021-0081
one meter gas cell fitted with KBr windows. Vapor spectra were obtained on
ferrocene in the region 400-3500 cm-l; ferrocene-d-10 in the region 400-3500 cm-l;
and ruthenocene in the region 700-3500 cm-l.
All infrared spectra obtained are reproduced in Figs. l-6. Infrared spectra of
ferrocene and ruthenocene were obtained in this laboratory as a check to solution
spectra in the region 700-3500 cm-l given in the literature [6-81.
Raman spectra were obtained using a Hilger 612 spectrograph. This is a two
prism instrument which records photographically, having a camera aperture of
f/5*4. Raman spectra in CS,, Ccl,, CHCl, and benzene solutions were obtained.
Spectra on ruthenocene were obtained with both Hg 4358 A and 5461 A excitation
using the filters and photographic plates listed in Table 1 and Table 2. Ferrocene
absorbs throughout much of the visible region. Excitation was accomplished with
the Hg 5770-5790 A doublet as well as the Hg 5461 A line using the filters and
photographic plates listed in Table 1 and Table 2. Spectra on ferrocene and
ferrocene-d-10 were also obtained with the Na 5890-5895 A doublet. The Na
5890-5895 A excitation was accomplished with the use of a sodium vapor lamp
unit described elsewhere [9].
It was found that the intensity of the Raman scattering for ferrocene was
rather sharply dependent on the concentration. Attempts to obtain Raman
spectra on highly concentrated ferrocene solutions gave very poor results. This

308
 The vibrational spectra and structure of ferrocene and ruthenocene

40
I I I Y I I III I Y II I I I I I I
20 I I 1 I / I” I I ,. , I I I /

6
‘si 0
n 300 400 500 600 700 800 900 1000 1100 1200 1300 1400
.- 1500 1600

E Wavenumber cm-’

1
60
stab Solution Cdl (a 0.031 cm
mnpemture 25.C kn.qta
1b1O.032 cm
40

20
Labcmtory

&O
I 1500
I 1600
I l70J
I BOO
I 22200
I 2400
I 2600
I 2800
I 3OOO
I 5200
I 3400
I 3600
I I

Wave number cm -’

Fig. 1. The infrared spectrum of ferrooene in solution.

(a) 0.45 M in Ccl, (b) 0.22 M in Nujol solution.

loo
1

01 I I I I I I I I
I
I
I
I
I
1
I
200 300 400 5oo 600 700 800 900 low no0 1200 13 Do WOO 15OO 1600
Wave numbers
100

80

60

20

I I I I I I
?&Xl 1600 1700 l&DO 2000 2200 2400 2600 2000 3000 3200 3400

Wave numbers cm-’

Fig. 2. The infrared spectrum of ferrocene vapor.

309
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

80

60
40 V II V

Wave numbers

stat4 Solution
Thn~mlurc25.C k$tkI0*035cm

01 I I I I I I I I I I I I
1500 l600 l700 1800 200022oO2400 26002&X3OOo320034OO360~
Wave numbers cm-

Fig. 3. The infrared spectrum of ferrocened-10 in solution; 400 -6OOcm-*, 0*16M in

Nujol solution; 600-800 cm-l, 0.32 M in CS,; 800-3400 cm-l, 0.45 M in Ccl,.

x 200 300 400 500 600 700 800 lOO0 llO0 1200 1300 1400 1500 1600 17 lo
Wave numbers

100 1 Compound
Ferrocene-d-l0
80

60

40

20

1
&O 1600 l700 l.900 2000 2200 2400 2600 2800 3000 3200 3400
Wove numbers cm-’

Fig. 4. The infrared spectrum of ferrocene-d-10 vapor.

310
 The vibrational spectra and structure of ferrocene and ruthenocene

100
s
60

60

c
.g ‘41
.E 200 300 400 500 600 700 a00 900 1000 no0 1200 1300 1400 1500 1600 1700
E Wave numbers cm-’
t
F
I-
Compound
I Ruthenocene
80 /“/ Source and purity

60
state Solution Cell
T~~~PJ~~IV 25’C length O-052cm
40

20
LabomCay

0
l5OOl6001700 180020002200240026002600300032003400
Wave numbers cm-’

Fig. 6. The infrared spectrum of ruthenocene in solution; 400-600 cm-l, O-035 M in

Nujol solution; 600-950 cm-l, 0.035 M in CS,, 950-3400 cm-‘, 0.05 M in Ccl,.

I
20

c
.g 0200 300 400 500 600 700 800 900 looo 1100 1200 1300 1400 1500 1600 1700
Wave number cm-’

100

80

60

40

20
I
$0 1600 1700 1800 2000 2200 2400 2600 2800 3000 3200 3400
Wave number cm-’

Fig. 6. The infrared spectrum of ruthenocene vapor.

311
 ELLIS R. LIPPINCOTT
and RICHARD
D. NELSON

Table 1. Filters for Raman spectra using different excitation wavelengths

Hg excitation High frequencies Low frequencies

:-

4358 A dilute Rhodamine saturated NaNO,

(5 DGN extra)
dilute PrCl,
5461 A saturated NdCl, saturated KsCrO,
saturated NiSO,
5770-5790 A saturated NiSO, saturated K,Cr,O,

- i

Table 2. Photographic plates for Raman spectra using different excitation wavelengths

Hg excitation Photographic plates

4358 A Eastman Kodak 103 J backed

5461 A Eastman Kodak 103 AE backed
5770-5790 A Eastman Kodak 103 AE backed

was caused by the partial absorption of the exciting radiation before scattering
followed by the partial absorption of the Raman radiation after scattering. It
was also found that a maximum intensity for scattering was attained at a con-
centration considerably less than that of a saturated solution. A detailed descrip-
tion of this optimum concentration effect is given by FISHER [lo].
In order to obtain better filtering it was necessary to circulate a filter solution
instead of water through the cooling compartment of the filter cell. The Raman
tube was sealed to the bottom of the filter cell with rubber tape creating another
compartment which held filter solution. A fourth filter was gained by wrapping
the Raman tube with a Kodak Wratten filter number 55 when using Hg 5461 A
excitation. Iron spectra were used as a standard for reading the spectral plates.
The vibrational spectra of ferrocene, ferrocene-d-10, and ruthenocene are listed
in Table 3. Polarization measurements of the Raman spectra were not taken
because of the long exposure times required for such colored substances.

Frequency assignment
The distribution of the fundamental modes of vibration among the symmetry
species of the D,, character table is shown in Table 4. Raman active fundamentals
are in species Al,, E,, and E,, and infrared active fundamentals are in species
A,, and E,,. In the following discussion, modes which involve motion perpen-
dicular to the cyclopentadienyl rings will be designated by (I) and modes which
involve motion parallel to the rings will be designated by (II).
The assignment of frequencies corresponding to motion within the cyclo-
pentadienyl rings was facilitated by comparison to similar modes in benzene.
Frequencies due to ring-metal-ring vibrations were found to be roughly analogous
to frequencies observed for linear XY, molecules and were assigned accordingly.

312
 The vibrational spectra and structure of ferrocene and ruthenocene

Table 3. The vibrationr ectra of ferrocene, ruthenocene and ferrocene-d-10

-
Ferrocene Ruthenocene Ferrocene-d-10
-
Infra- I.R. Infra- I.R. Infra- I.R.
Raman Raman Raman
red vapor red vapor red vapor
___-

170m 291 m*
303 cm-irn* c 330 s 355 w’
388 w 402 m 457 5 462 s
478 s 480 s 446 s 485 s 476 s
492 s 496 s 528 w 614 w 637 s 638 m
782 w 776 u 763 w 770m 679 w 671 w
811 s 816 8 804 w 806 8 808 8 7718 775 s
834 w 840 u 835 w 840 w 849 m 846 m
1010 w 1002 8 1012 s 996 m 1002 s 1008 s 1049 sf 1044 s 1070 8
1060 w* 1051 w 1056 m 1050 w
1105 a* 1108 s 1104 s 1103 s 1105 s 1260 w 1270 m
1178 m 1188 w 1193 w 1290 m* 1290 m 1290 m
1356 w 1360 w 1334 m 1334 m
1408 m 1411 s 1416 v 1412 m 1413 m 1413 w 1358 m 1358 m
1560 vw t 1
1620 m 1620 n 1622 m 1618 m 1403 m 1403 m
1650 m 1644 n 1651 m 1640 m 1444 m 1444 m
1684 m 1680 n 1684 m 1690 m 2318 w
1720 m 1716 n 1727 m 1732 m 2335 s 2354 m 2354 m
/ 1758m 1748 n 1774 m 1775 m
3085 m 3089 m
3099 s 3085 s 3106 n

VW = very weak; w = weak; m = medium;

7 = obtained by Na radiation.
3104 8
-
3100 m

s = strong;
- 3108 m
-
* = obtained by Hg and Na radiation;
-
Table 4. Selection rules for &,d sandwich structure

Number of
Species Activity
frequencies

Al, R
A 1U inactive
Am inactive
A IR
E%
E
R
IR
174
Em R
E 2u inactive

R, Raman active; IR, infrared active.

The spectra of ferrocene-d-10 proved very useful for the frequency assignment
particularly in distinguishing between CC and CH modes. The ratio of the observed
frequencies in ferrocene to the corresponding frequencies in ferrocene-d-10 was
calculated. These values were compared to similar values for benzene in Table 6.

313
 ELLIS R. LSTTINCOTT and RICHARD D. NELSON

The Teller-Redlich product rule was used as a measure of the correctness of

the assignment of frequencies. Anharmonicity will cause the observed ratio of
frequency products to be slightly greater than the calculated ratio. Because
some of the frequencies in species E,, were not observed the product rule was
not applied to this species. The results of this calculation are as follows: species
A,, ratio observed O-524, ratio calculated 0.500; species A,, ratio observed O-537,
Table 5. Description of fundamental modes of vibration

Frequency
Species Description
number
-_

Al, 1 sym. CH stretching

2 sym. CH bending (I)
3 sym. ring breathing
4 sym. ring metal stretch

A IU 5 CH bend (II)
6 internal rotation

A 29 7 CH bend (II)

A 2u 8 CH stretching
9 CH bending (1)
10 antisym. ring breathing
11 antisym. ring metal stretch

E 10 12 CH stretching
13 CH bending (II)
14 CH bending (1)
15 sym. CC stretch
16 sym. ring tilt

E 114 17 CH stretching
18 CH bending (11)
19 CH bending (I)
20 antisym. CC stretch
21 antisym. ring tilt
22 ring metal ring bending

E 2s 23 CH stretching
24 CH bending (II)
25 CH bending (I)
26 CC stretch
27 ring distortion (II)
28 ring distortion (I)

E ea 29 CH stretching
30 CH bending 0))
31 CH bending (1)
32 CC stretch
33 ring deformation (II)
34 ring deformation (I_)

314
 The vibrational spectra and structure of ferrocene rend ruthenocene

ratio calculated 0.513; species El, ratio observed 0.368, ratio calculated 0.365;
species E,, ratio observed 0.401, ratio calculated O-363.
An examination of Table 3 shows several features which are consistent with
a molecule having D,, symmetry. The number of Raman and infrared frequencies
observed is rather small for a molecule having 57 vibrational degrees of freedom.
The selection rules for a molecule with D,, symmetry predict the appearance of
15 Raman and 10 infrared fundamental vibrational frequencies. D,, selection
rules are also followed by the model in which free internal rotation is occurring
(cf. BAUMAN R. P. J. Chem. Phys. 1956 24 13).
D,, symmetry would require planar rings with equivalent bonds. This would
predict that only one type of CH bond is present. Consistent with this is the
appearance of only one type of CH frequency in either the infrared or Raman
spectrum. The appearance of multiple bond frequencies near 1410 cm-l and
1560 cm-l is further evidence for equivalent multiple bonds which result from
the delocalization of the r-electrons.
Examination of Table 3 shows some rather unusual features in the vibrational
spectra of ferrocene and ruthenocene. For example, many of the infrared and
Raman frequencies are coincidences or near coincidences. However, since a DBd
model has a center of symmetry, the rule of mutual exclusion should hold [l I].
The fact that coincidences do exist was interpreted to mean that the symmetric
and antisymmetric modes of vibration involving displacements associated with
the cyclopentadienyl rings show little interaction. Consequently these coincidences
were assigned to the CH and CC modes of vibrations. Also requiring explanation
is the appearance of the band systems around 1700 cm-l in the infrared spectrum
of both ferrocene and ruthenocene. It is not believed that these frequencies can

9xx/ ’ /
/’

‘/ I\’
\’

&J \
\
\
\

Fig. 7. Dsd model.

be interpreted in terms of fundamental modes of vibration, for if they were similar

frequencies should appear in the Raman spectra. Also, the D,, model has no
structural features that would lead one to predict the appearance of fundamental
vibrations in this region. This band system was originally interpreted as being
related to the restricted rotation of the cyclopentadienyl rings with respect to one
another [l]. However, examination of the position of this band system in ferrocene-
d-10 reveals that it extends from 1290 cm-l to 1444 cm-l. This represents shifts
by factors of 1.21 to 1.25 which would imply that these bands are associated with

315
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

Table 6. Frequency shifts produced by substituting D for H in ferrocene

Type vibration V&l

‘AD,

CH stretching 1.30-1.35 1.31-1.34

H (II) bending 1.20-1.28 1.3
H (I) bending 1.20-1.28 1.22-1.3
CC stretching 1.05 1.09-1.1
Ring breathing 1.05 1.05-1.06
C (II) bending 1.05
C (JJ bending 1.1
Ring metal stretch 1.04
Ring tilt 1~01-1~09

CH modes (Table 6) and not hindered rotation. Benzene and its substituted
derivatives show similar bands which have been interpreted as overtones and
combination bands involving CH modes [12]. Because of these facts the band
system in ferrocene and ruthenocene is interpreted as combination and overtone
bands involving CH modes. No completely satisfactory assignment has been
made for these bands.
Comparison of the ferrocene and ruthenocene spectra show that frequencies
due to vibrations within the rings are at essentially the same position, whereas
frequencies due to ring-metal-ring vibrations occur at different positions. This
was interpreted to mean that the strength of the CC and CH bonds are essentially
of the same magnitude in the two compounds, whereas the strength of the ring-
metal bonds is different. The ring-Ru-ring symmetric stretching frequency occurs
at 330 cm-l, whereas the ring-Fe-ring symmetric stretching frequency occurs at
303 cm-l, indicating the rings are bound more tightly to the ruthenium atom than
to the iron atom. The ring-Ni-ring symmetric stretching frequency has been
calculated to be at 200 cm-r indicating that the rings are bound less tightly to the
nickel atom than to either the iron or ruthenium atom.
A frequency assignment is also given for nickelocene, Ni(C,H,),. This assign-
ment is somewhat more empirical than that for ferrocene or ruthenocene in that
no Raman spectrum was obtained. More emphasis was placed on the positions of
infrared frequencies and comparisons to ferrocene and ruthenocene. The frequency
assignment was carried out for nickelocene in order that the thermodynamic
functions could be calculated and compared with the corresponding functions
for ferrocene and ruthenocene.

A,, Species (Ruman)

A,, frequencies are generally strong, sharp, and polarized. Frequencies which
received immediate consideration because of their intensity were 3099 cm-l and
1105 cm-l in ferrocene and 3104 cm- l, 1104 cm-l and 330 cm-l in ruthenocene.
The totally symmetric CH stretching frequency occurs at 3062 cm-l in benzene
and is quite intense. The 3099 cm-l band in ferrocene and 3104 cm-l band in

316
 The vibrational spectra and structure of ferrocene and ruthenocene

ruthenocene were assigned to ol. The ferrocene 3099 cm-l band shifted to 2335
cm-l in ferrocene-d-10.
The symmetric ring breathing mode occurs at 992 cm-l in benzene. It is ex-
pected that the frequency due to this mode in ferrocene and ruthenocene would
occur somewhat higher due to the fact that the five-membered ring has a smaller
C-C-C angle than in benzene, as well as to the influence of the metal-ring bonds.
The frequencies 1105 cm-l in ferrocene and 1104 cm-r in ruthenocene were of
comparable intensity and sharpness to the 992 cm-l frequency in benzene and
were assigned to wQ. The 1105 cm-l ferrocene frequency shifted to 1049 cm-l in
ferrocene-d-10. This is only a shift by a factor of I.05 which is typical of CC modes.
This assignment was also suggested by the occurrence in the infrared spectra of
frequencies of similar position and intensity which could be assigned to the anti-
symmetric ring breathing mode.
The 330 cm-l frequency was the lowest band obtained in the Raman spectra
of ruthenocene. The corresponding frequency in ferrocene occurred at 303 cm-l.
These frequencies are undoubtedly due to similar modes of vibration in the two
compounds. The two modes remaining to be assigned in this species are w2 CH
bend (I) and wq ring-metal stretch. The 303 cm-l ferrocene frequency shifts to
291 cm-l in ferrocene-d-10. This shift is by a factor of 1.04. The ferrocene 303
cm-l frequency and the ruthenocene 330 cm-l frequency were assigned to 04.
If the two rings are considered as having their mass at the center of mass of the
ring then wq is a linear XY, type mode.
The w2 CH bend (I) remains to be assigned. This mode is infrared active in
benzene and occurs at 671 cm-l with high intensity. The infrared spectra of both
ferrocene and ruthenocene contained intense bands at approximately 800 cm-l
which were established to be CH modes (see the assignment for species A,,).
The appearance of these infrared bands suggested that similar bands should appear
in the Raman spectra. Solvent bands in this region made the detection of bands
practically impossible. The broadness and increased intensity of a solvent band
in the ruthenocene spectra indicated a frequency at 806 cm-l. Ferrocene-d-10 has
a band at 614 cm-l. No Raman bands were observed in ferrocene from 500 cm-i to
1000 cm-l. If the 614 cm-l ferrocene-d- 10 frequency had shifted from 1000 cm-i in
ferrocene the shift would be by a factor greater than 1.6 which is unreasonable in
that the largest possible shift is by a factor of 1.41. The infrared bands at approxi-
mately 800 cm-l in ferrocene shifted to 630-680 cm-l in ferrocene-d-10 suggesting
the 614 ferrocene-d-10 Raman band shifted from approximately 800 cm-l. These
shifts agree reasonably well with those observed for benzene. On this basis w2
was assigned values of 804 cm-l in ferrocene and 805 cm-l in ruthenocene.
The assignment of nickelocene frequencies to the species A,, was based solely
on infrared positions and the A,, assignment for ferrocene and ruthenocene. o1
was assigned a typical value of 3100 cm-l. A strong infrared band at 770 cm-l
which had structural features similar to the 800 cm-l bands in ferrocene and
ruthenocene led to the assigning of 770 cm-l to w2. w2 has an appreciably lower
value in nickelocene than in ferrocene or ruthenocene. This may be due to a
combination of factors. The ring metal distance in nickelocene is greater than it
is in ferrocene or ruthenocene which might cause the rings to be more aromatic in

317
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

nickelocene. Weakly bound rings would cause the CH and CC frequencies to be-
come more benzene-like. Also, since the ring-metal bond is weaker in nickelocene
than it is in ferrocene or ruthenocene wa may not be perturbed in nickelocene to
the extent it is in ferrocene or ruthenocene. The infrared spectra also contained a
strong band at 1110 cm-l. o3 was assigned a value of 1105 cm-l o4 was assigned
a value of 220 cm-l for reasons that will be discussed in the A,, assignment.

A,, Species (inactive)

The modes of vibration in this species are wg, CH bend (II), and u)~ an internal
rotation.
The fundamental in benzene similar to oh is also inactive but has been cal-
culated to have a value of 1190 cm-l. co5 was assigned a value of 1200 cm-l in
ferrocene, ruthenocene, and nickelocene. This assignment is thought to be justified
on the basis of the position of other CH (II) bending modes. These modes have
frequencies which are reasonably close to the frequencies due to corresponding
modes in benzene (see assignment for w13, ml8 and w&. mo6was assigned to free
internal rotation. Several investigators have suggested that no barrier to internal
rotation exists [13-l 41.

A,, Species (inactive)

Species A,, contains only one fundamental mode of vibration, a o, CH bend
(II). This mode is analogous to wg. On the basis of the assignment for o5 and
following the observation that symmetric and anti-symmetric CC and CH modes
show coincidence, cuI was also assigned a value of 1200 cm-l for ferrocene, rutheno-
cene and nickelocene.

A,, Species (infrared)

The four fundamental modes of vibration in this species involve the same type
of motion as the four modes in species A,,. Because of the similarity between
symmetric and antisymmetric CC and CH modes it would be expected that os,
c+,, and oiO would be coincident or nearly coincident with wi, u)~,and oa respectively.
A check of Table 3 reveals that infrared frequencies for both ferrocene and
ruthenocene were observed that are coincidences or near coincidences with the
frequencies in the Raman spectrum assigned to modes or, w2, and oa. The 3085 cm-l
frequency in ferrocene and the 3100 cm-l frequency in ruthenocene can obviously
be assigned to 0s.
There are a number of infrared frequencies that would fit wg. They are 782 cm-l,
811 cm-l and 834 cm-l in ferrocene and 763 cm-l, 806 cm-l and 835 cm-l in
ruthenocene. Comparison of the ferrocene spectra to the ferrocene-d-10 spectra
shows that the ferrocene 782 cm-l frequency can not be readily interpreted as a
fundamental CH band. The 811 cm-l ferrocene band and the 637 cm-l ferrocene-
d-10 band are due to the same mode of vibration. Likewise the 835 cm-l ferrocene
band and the 679 cm-l ferrocene-d-10 band are due to the same mode of vibration.
The shifts in these bands from ferrocene to ferrocene-d-10 are by factors of l-27
and l-22 which are characteristic of this type of CH mode. If the 782 cm-l band
shifted by a similar amount, a third band should appear about 600 cm-l or greater

318
 The vibrational spectra and structure of ferrocene and ruthenocene

in ferrocene-d-10. Since a third band did not appear, the 782 cm-l band was not
interpreted as a CH fundamental. It will be seen later that 782 cm-l band in
ferrocene and 763 cm-l band in ruthenocene can be conveniently interpreted as
combination bands. We now have the choice of assigning 811 cm-l, 806 cm-l or
835 cm-l, 834 cm-l to 09. An examination of the vapor spectra of ferrocene and
ruthenocene shows that the ferrooene 811 cm-l band and the ruthenocene 806 cm-l
band are very intense and show P&R structure and are probably parallel bands.
Nondegenerate modes of vibration in a symmetric top molecule give rise to parallel
bands. The only infrared active nondegenerate species is A,,. Therefore 806 cm-l
in ruthenocene and 811 cm-l in ferrocene must be assigned in species A,,. Since
they are CH bending modes the only assignment that can be made for 811 cm-l in
ferrooene and 806 cm-l in ruthenocene is wg.
The appearance of an intense frequency at 1108 cm-l in ferrocene and 1103 cm-l
in ruthenocene suggested that these may be ring breathing frequencies coincident
with the Raman active cc)amodes. The 1108 cm-l ferrocene band shifted to 1044
cm-l in ferrocene-d-10. This was by a factor of 1.06 which compared favorably to
the shift observed for o3 and also to the shift observed for the similar mode in
benzene. The vapor spectra of ferrocene and ruthenocene reveal that the 1108 cm-l
ferrocene band and the 1103 cm-l ruthenocene band also show P&R structure and
are therefore parallel bands.
wrl is another XY, type mode. For molecules of this type the following
expression approximately holds.

In the case of bis-cyclopentadienyl metal compounds M, is the total mass of a

ring and M, is the mass of the metal atom. The observed ratio is generally less
than the calculated ratio due to anharmonicity. Since wq is 303 cm-l for ferrocene
and 330 cm-l for ruthenocene, 478 cm-i and 492 cm-l for ferrocene and 446 cm-l
for ruthenocene approximately fit the above relationship. Therefore, oll can be
assigned to 446 cm-l for ruthenocene. The ferrocene 478 cm-l frequency corre-
sponds to the ruthenocene 446 cm-l frequency and was therefore assigned to oii.
This assignment agrees well with the ferrocene-d-10 spectra. The 303 cm-l and
478 cm-l ferrocene frequencies shift to 291 cm-l and 457 cm-r in ferrocene-d-10.
As might be expected both shifts are by a factor of 1.04.
Once the ferrocene and ruthenocene frequencies had been assigned for species
A,, the nickelocene assignment was straightforward for its infrared spectra is very
similar to that of ferrocene and ruthenocene. The frequency at 3075 cm-l was
assigned to mo8. The nickelocene 773 cm-l band was similar in appearance to the
ferrocene 806 cm-l band and was therefore assigned to wg. The later reasoning
also led to the assignment of the nickelocene 1110 cm-l band to wl,,. These fre-
quencies are due to CC or CH modes and would not be expected to change much
from molecule to molecule. Frequencies due to linear XY, type modes, however,
would be expected to vary from molecule to molecule as the metal atom is changed.
Therefore, the linear XY, type modes can not be assigned on the basis of coin-
cidences. The frequency observed at 355 cm-l in nickelooene was similar to the

319
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

478-492 cm-l pair observed in ferrocene and ivas assigned to CC)~~.The basis for
assigning 220 cm-l to wq in nickelocene can now be explained. The mass of a
nickel atom is only slightly different from the mass of an iron atom. From the
relationship for linear XY, type molecules the ratio co1J04 would be expected to
be approximately the same for ferrocene and nickelocene. On this basis a value
of 220 cm-l was calculated for 04.

E,, Species (Raman)

The ferrocene 3085 cm-l band and the ruthenocene 3089 cm-l band were
assigned to oia. The ferrocene 3085 cm-l band shifted to 2318 cm-l in ferrocene-
d-10.
The mode in benzene which is similar to oi3 in ferrocene and ruthenocene is
infrared active and gives an intense band at 1037 cm-l. Two ferrocene frequencies
1010 cm-l and 1050 cm-l, and two ruthenocene frequencies, 996 cm-l and
1056 cm-l, are in the vicinity of the benzene band. Raman frequencies due to
vibrations in species E,, would be expected to have coincidences in the infrared due
to vibrations in species E,, since the CH and CC modes involve the same type of
motion in both species. Inspection of the observed frequencies shows that all of
the above bands have coincidences in the infrared spectrum. However neither the
ferrocene 1057 cm-l infrared band nor the ruthenocene 1050 cm-i infrared band
were observed in the vapor spectrum indicating they are not due to active funda-
mental modes. The ferrocene 1010 cm-l band and the ruthenocene 996 cm-l band
were assigned to oia.
The mode in benzene similar to o14 gives a band at 849 cm-l. A band was
observed in the Raman spectra of ruthenocene at 804 cm-l. Ferrocene and
ruthenocene both had infrared frequencies which could be interpreted as near
coincidences with Raman bands near 800 cm-i. The ruthenocene 806 cm-l fre-
quency was assigned to o14. w14 in ferrocene was assigned a value of 800 cm-l.
A normal co-ordinate analysis of the five-membered ring also led to a prediction
of 800 cm-l for m14.
co15corresponds to a symmetric CC stretching mode of vibration. The frequency
due to a similar vibration in benzene is infrared active and occurs at 1485 cmrl.
This benzene frequency shifts by a factor of 1.1 to 1333 cm-l in benzene-d-6.
Ferrocene and ruthenocene have Raman bands at approximately 1410 cm-l which
have coincidences in the infrared as would be expected. The ferrocene 1408 cm-l
band shifts to 1290 cm-l or by a factor of 1*09inferrocene-d-10. Therefore 1408 cm-l
in ferrocene and 1412 cm-l in ruthenocene were assigned to e+,.
oi6 a symmetric ring tilt mode, was expected to have a low frequency and to
be shifted only slightly from ferrocene to ferrocene-d-10. The remaining low Raman
frequencies are 388 cm-l in ferrocene and 402 cm-l in ruthenocene. These were
assigned to o16. The 388 cm-l ferrocene band shifted to 355 cm-l or by a factor
of 1.09 in ferrocene-d-10.
The nickelocene frequencies were again assigned by comparison with the
assignments for ferrocene and ruthenocene and comparison with nickelocene
infrared bands. Infrared bands available are 3075 cm-l, 1000 cm-l, 1430 cm-l and
800 cm-l. o12 was assigned a value of 3085 cm-l. wla was assigned a value of

320
 The vibrational spectra and structure of ferrocene and ruthenocene

1010 cm-l. This is slightly higher than the observed infrared band as is oi3 in the
two other compounds. w14 for ferrocene and ruthenocene is similar to w2 and wg.
o14 was assigned a value of 770 cm-l. w15 was assigned a value of 1425 cm-l
which is slightly less than the observed infrared band as is o15 in the other two
compounds. o16 was assigned strictly on the comparison with ferrocene. The
ratio oJw~~ was calculated for ferrocene. Assuming the ratio to be the same for
nickelocene ols would have a value of 275 cm-l.

Species E, ,, (infrared)
There are six frequencies associated with this degenerate species. ol, was
assigned typical values of 3075 cm-l for ferrocene and 3100 cm-i for ruthenooene.
Ferrocene and ruthenocene both had infrared .bands at 1002 cm-l. The ferrocene
1002 cm-l band shifted to 771 cm-l or by a factor of 1.3 in ferrocene-d-10 indicat-
ing that it is a CH mode. The 1002 cm-l band was assigned to o18 for ferrocene
and ruthenocene.
The ferrocene 834 cm-l band and the ruthenocene 835 cm-l band have been
interpreted as near coincidences with Raman bands near 800 cm-l. The ferrocene
band shifted by a factor of 1.22 to 679 cm-l in ferrocene-d-10 indicating a CH
mode. These bands were assigned to or9.
The 1411 cm-l frequency in ferrocene and 1413 cm-l frequency in ruthenocene
were assigned to 02,,. The ferrocene 1411 cm-l band shifted by a factor of 1.10 to
1260 cm-l in ferrocene-d-10.
The frequency due to cozl is expected low. The shift of cc)21from ferrocene to
ferrocene-d-10 would also be expected to be small as for or6. The 492 cm-l fre-
quency in ferrocene and 528 cm-l frequency in ruthenocene were assigned to c+r.
The ferrocene 492 cm-l band shifted by a factor of 1.01 to 485 cm-i in ferrocene-
d-10 which was expected.
oz2 is the degenerate linear XY, bending mode of vibration. This is the lowest
fundamental frequency that occurs in linear XY, molecules. It was noted that
this vibration in CO, and CS, had a frequency that was roughly half the frequency
for the symmetric X-Y stretch. On that basis CI+~would be expected to have a
value in the neighborhood of 150 cm-l for ferrocene. A band was observed at
170 cm-l in ferrocene by PALIK [15] and was assigned to ws2. os2 for ruthenocene
was calculated with the aid of the ratio 04/oz2 observed in ferrocene. This yielded
a value of 185 cm-l.
The frequencies in nickelocene available for assignment to species E,, were
mentioned in the E,, nickelocene assignment. These frequencies were assigned as
follows: oi6 to 3075 cm-l, 1000 cm-l to oi8, 800 cm-l tee+,, 1430 cm-l to wz,,.
The intensity and structural features of the 355 cm-i band led to the interpretation
that it was similar to the 478-492 cm-l pair in ferrocene, and 355 cm-l was also
assigned to 02i.
oz2 was assigned in the same manner discussed for ruthenocene. The value
calculated for ws2 was 125 cm-l.

EF,,Species (Ruman)
This species is degenerate and has six fundamental frequencies.

321
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

The typical values of 3085 cm-l for ferrooene and 3089 cm-l for ruthenocene
were assigned to wZ3. The mode in benzene similar to ws4 has a frequency of
1178 cm-l. The ferrocene 1178 cm-l band and the ruthenocene 1193 cm-l band
were assigned to o+*.
The Raman spectra of ruthenocene contained a band at 1056 cm-l and the
spectra of ferrocene contained a band at 1050 cm-i. The ferrocene 1050 cm-l band
shifted by a factor of I.25 to 849 cm-l in ferrocene-d-10 indicating that it is a CH
mode. Therefore 1050 cm-l in ferrocene and 1056 cm-l in ruthenocene were
assigned to oZ5.
The frequency in the Raman spectrum of benzene due to a mode similar to
ws8 is at 1584 cm-l, indicating that the ferrocene 1560 cm-l band should be
assigned to os6. A similar assignment was made for ruthenocene.
02, and ws8 were originally assigned values 900 cm-l and 500 cm-l respectively
strictly on the basis of comparison with benzene [2]. Theoretical calculations how-
ever predicted that w2, would have a value of 880 cm-l for ferrocene. Infrared
studies of ferrocene crystals by WINTER [16] yielded frequencies of 885 cm-l and
569 cm-l which were assigned to co3a and os4 respectively. It would be expected
that cos3 and ws4 would be coincident with ws7 and ms8. Therefore w2, and ws8
were assigned values of 885 cm-l and 569 cm-l respectively for ferrocene and
ruthenocene.
The nickelocene assignment for this species must be made purely on the basis
of frequency positions for corresponding modes in ferrocene and ruthenocene.
The values assigned correspond quite closely to the values in ferrocene and rutheno-
cene. They are os3 = 3085 cm-l, wZ4 = 1180 cm-l, os5 = 1050 cm-l, wZB = 1560
cm-l, 0.+, = 885 cm-l and 02s = 569 cm-l.

Species E,, (inactive)

Because this species is inactive, assignment of frequencies was made on the
basis of coincidences between symmetric and antisymmetric modes. None of the
modes in this species and species E,, involve motions which are associated with
the central atom. Since the modes in species E,, involve the same type of motion
as the modes in species Esu, the frequencies in these two species would be approxi-
mately at the same cm-i values for corresponding modes of vibration. On the
basis of this argument the following approximate assignment was made for all
three compounds. oZg = 3100 cm-l, oa,, = 1170 cm-l, ma1 = 1050 cm-l, 033
= 1560 cm-l, w33 = 885 cm-l, and 034 = 569 cm-l.

Assignme@ of observed non-fundamental frequencies

Frequencies that were not assigned to active fundamental modes of vibration
are the Raman 1356 cm-l band and the infrared peaks 782 cm-l, 1051 cm-l, and
1188 cm-i in ferrocene and the Raman 1360 cm-l band and infrared 763 cm-l peak
in ruthenocene.
The 1356 cm-l and 1360 cm-l bands can be assigned as the combination
u)~ + w25. The symmetry requirements are A,, x Ezs = E,, or that the com-
bination band be Raman active.
The ferrocene 782 cm-1 band and the ruthenocene 763 cm-l band can be

322
 The vibrational spectra and structure of ferrocene and ruthenocene

assigned as CC)~ + oll. Since A,, x A,, = A,, this combination would be infra-
red active. If this is applied to ferrocene-d-10 a band would be predicted in
the neighborhood of 748 cm-l. The 771 cm-l solution band and the 775 cm-l
vapor band are broad. This broadness may be due to a band slightly lower than
770 cm-l which could be CC)~ + oll combination.
Attempts to assign the ferrocene 1051 cm-l infrared band to a combination
have met with little success. oz2 + wz7 or oz2 + oa3 would explain this band.
However nickelocene also has a weak infrared band at 1050 cm-l which can not be
explained by this assignment. This ferrocene band does not appear in the vapor
spectra. It is believed that the appearance of this band is due to a breakdown of
the selection rules. Since a Raman band at 1050 cm-l was assigned in species Ezg
it is reasonable to assume that it would have a coincidence in species E,,. The
ferrocene crystal which has Cj symmetry produced a very intense infrared band
at 1050 cm-l [IS] and the 1050 cm-l solution band might be due to ozl. This
would also explain the appearance of an infrared band at 1050 cm-l in nickelocene
smce osl would not be expected to vary much from molecule to molecule.
The ferrocene 1188 cm-l infrared band might also be explained in the same
manner since a coincidence with os4 would be expected in the inactive species E,,.
A band was observed in the crystal at about this position and was assigned by
WINTER to 03,, which would be coincident with os4. 1188 cm-l might also be the
combination o16 + wg since A,, x E,, = E,, which would make the combination
infrared active.
The 846 cm-l band observed in the vapor spectrum of ferrocene-d-10 was due to
impurity arising from the decomposition of the gaskets of the gas cell.
WINTER made an independent frequency assignment based on the infrared
spectra of ferrocene crystals and vapor. As stated previously the crystal has Ci
symmetry and because of this the inactive infrared modes for a D,, point group
are active. WINTER observed and assigned frequencies to species A,, and E,,.
The values postulated for these species in the above assignment agree reason-
ably well with what those observed for the crystal. For example, o5 was
postulated to be 1200 cm-l and was observed to be 1257 cm-l; 02, was postulated
to be 900 cm-l, calculated to be 880 cm-l and observed to be 885 cm-l; and wz8
was postulated to be 500 cm-l and observed to be 569 cm-l.
The complete assignment of frequencies to the fundamental modes of vibration
is given in Table 7. The assignment of observed ferrocene-d-10 frequencies is also
given in this table.

Normal co-ordinate analysis

A successful completion of normal co-ordinate analysis of the tropylium ion,
(C,H,)+, provided interesting results [17]. Specifically it was found that the valence
force symmetry constants compared quite favorably with those of benzene and it
was concluded that the tropylium ion must be a planar, aromatic 7-membered
ring. Since ferrocene contains planar, aromatic 5 membered rings, a similar analy-
sis on the ferrocene cyclopentadienyl rings may yield interesting comparisons
among the 5-, 6- and 7-membered aromatic rings.
It was decided to employ the Wilson FCI method [18] for the analysis of a

323
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

Table 7. Assignment of frequencies for ferrocene, ferrocene-d-10, ruthenocene

and nickelocene
- -
Species RuKW,), Ni(C,H,),
- - - _

Al, 1 3099 2335 3104 (3100)

2 (604) 614 (805) (770)
3 1105 1049 1104 (1105)
4 303 291 330 (220)

A 1U 5 (1200) 1257b (1200) (1200)

A28 7 (1200) (1200) (1200)

A 2u 8 3085 2354 3100 3075

9 811 637 806 773
10 1108 1044 1103 1110
11 478 457 446 355

-f-L 12 3085 2318 3089 (3085)

13 1010 (771) 996 (1010)
14 (800)a (614) 804 (770)
15 1408 1290 1412 (1425)
16 388 355 402 (275)

E 1U 17 3075 2354 3100 3075

18 1002 771 1002 1000
19 834 679 835 800
20 1411 1260 1413 1430
21 492 485 528 355
22 170 (162) (185) (125)

E2s 23 3085 2318 3089 (3085)

24 1178 (1045) 1193 (1180)
25 1050 849 1056 (1050)
26 1560 (1540) (1560) (1560)
27 (900) 880” (640) (900) (900)
28 (500) (465) (500) (500)

E 2u 29 (3100) (3100) (3100)

30 (1170) (1170) (1170)
31 (1050) (1050) (1050)
32 (1560) (1560) (1560)
33 (900) (900) (900)
34 (500) (500) (500)
- - -
( ) means unobserved.
Superscript “a” means calculated by a normal co-ordinate analysis.
Superscript “b” means observed in crystal.

324
 The vibrational spectra and structure of ferrocene and ruthenocene

ferrocene ring, (C&H,). The analysis of (C,H,) was greatly simplified because many
of the methods worked out for (C,Hc) could be used for (C&H,) [ 191. A preliminary
report of this work has been given previously.
Table 8. Distribution of observed frequencies
in ferrocene rings of Dsh symmetry

Species Frequencies

0 12 = w17
0 13 = %
w15 = 020

El" ml4 = WI9

w 23 = O29
E2'
a24 = 030
w26 = w32
0 27 = O33

Table 9. Symmetry co-ordinates for a ferrocene Dsh cyclopentadienyl ring

I CoeEicient j I I
Species VFC
4

Al’ 1 1 1 s
1 1 1 1 t
1 ! I
A,” 1 / 1 ~ 1 1 1 1’
El’ 1 I Cl ~ C2 C2 Cl S
0 1 -cc3 Cl -cc2 c2 -c !l C2 - 1 0.3326 P
1 + Cl Cl + C2 XC2 Cl + c I2 t
El” 1 1 c2 c2 Y
E2’ 1 ( :: Cl cl

1 c2 I :: Cl C2 ( d/(2/5) S
0 I 1 -Cl cr - CI Cl - C2 Cl - 1 0.538 P
lf Cl I c’7 + CI 2Cl C2 + Cl 1+c2 1.023 t

N = Normalization factor; Cl = cos +; C!? = cos 2$; 4 = 360”/5

The FG method involves the solution of the secular equation

IF - G-111= 0
where F is the force constant matrix, G the kinetic energy matrix and 1 is the

6 325
 ELLIS R. LIPPINCOTT and RICHARD D. NELSON

diagonal frequency matrix. The methods of evaluating the elements of G and

solving the secular equation are described by WILSON et al. [18].
A C&H, ring has D5,, symmetry. It is important to knod in which species of
the D,, character table the observed ferrocene ring vibrations will occur. This
information is presented in Table 8.

Table 10. Comparison of valence force symmetry constants for the

cyclopentadienyl, tropylium ion and benzene rings
--

=‘YP~

CH stretching
T
-4.93 x 105
C,H,‘b~~’
VFSC

5.12 x 105
(C,H,+)‘V)

5.16
VFSC

x lo6
CC stretching 6.97 x lo6 7.62 x lo6 7.66 x lo6
CH (I) bending 0.42 x lo-” 0.228 x lo-” 0.256 x lo-”
CH stretching 5.18 x 106 6.15 x 106 5.00 x 106
CC stretching :; 3085
1411 3099
1485 3026
1477 5.50 x 105 6.14 x lo5 7.40 x 106
CH ([I) bending 14 1002 1037 992 0.96 x lo-” 1.02 x 10-n 0.96 x lo-”
CH stretching 5.218 x lo5 5.04 x 106 5.18 x lo5
CC stretching :: 3085
1560 3047
1596 3075
1594 5.50 x 106 5.66 x 106 6.09 x lo6
CH (I ) bending
CC (I ) bending
-0.95
1.78
x
x
10-n
lo-”
-
0.99
1.45
x
x
lo-‘1
10-n

Ia) Frequency number 11, the Raman active CH bending mode, was not observed in the spectra,
()) CRAWFORDB. L. and MILLER F. J. Chem. Ph,ys. 1949 17 249. tc) Stretching and bending VFSC are
1.16
1.02
x
x
10-n
IO-”

in units of dyn/cm and dyn cm respectively. cd)For C,H,+ the Ft,q interaction constant has values of
2.36 x 10es dyn and 0.22 x 10-s dyn in species E,’ and E,’ respectively. For C,H, the Ft@ interaction
in species E,’ has a value of 2.10 x 1O-3 dyn.

In the following, the subscripts a refer to ring distortion modes (II), /? to CH

bending modes (I)), y to CH bending modes (I), s to CH stretching modes, and t to
CC stretching modes.
The symmetry co-ordinates calculated for use in the analysis are givenin Table 9.
Expressions for the G elements and their calculated values are given in Tables 11
and 12.
The unobserved frequency w14 was calculated by a slight adjustment of the
force constant of benzene.
The results of this analysis are given in Table 10. Also given in Table 10 are
the valence force symmetry constants for C,H, and (C,H,)+.
A detailed normal co-ordinate analysis for the entire ferrocene molecule
rather than just the cyclopentadienyl rings will be given in a separate publication.

Comparison of force constants

A comparison of the force constants and frequencies of the 5-, 6- and 7-membered
(CH) rings is shown in Table 9. Observations which can be drawn from Table 9
are :
(1) The values of the frequencies of the ring breathing modes w2 and oi,, are
progressively smaller from the 5- to the ‘I-membered ring, whereas the values of
the force constants are progressively larger. This frequency depends to a large
extent on G,, which is dependent on the C-C-C angle. This angle changes from
108” for (C,H,)- to 120’ for C,H, to 128” for (C,H,)+.

326
 The vibrational spectra and structure of ferrocene and ruthenocene

(2) The force constants for the CH stretching fundamentals agree quitg well
among the 3 ring systems indicating that the ferrocene cyclopentadienyl CH bond
is an aromatic type CH bond.

Table 11. B elements for Dbh C,H, ring

Species
_.. __..---
T
_!-
G elements

4’

A," Q,, = gyl c 2Yy2 -t- 3g,3

El’ G8.9= s,’

aft=L-1
+YmJ
Et1 -I- cos#) g,l -I- (cos#J-I- cos 2#)s,zf fl -I- cos+&t21

tr,, = [ l-‘,o*J[(l 00s 2$)g$ + (CO8I# - eos 2c#)gp3+ jeos 2# - ax3 ,p)g$
-
-k (CO824 - l&@l
G,, = [0.3QOQ~~(Z~5)1 2(1 -i- MM$I@,$
Css = [0.3326~~(2/5)] 2(1 - COB2$)gs,$
GtB = (0.3326)~(0.3909) (1 + co8 #f[ - (1 - 00s 2+)g,B’ + (cos # - 008 2+)gtf12
- (COB2g, - CO8$)gt# - (CO82ip - l)g,$]
El” GY$ = gv’ + 2 COB#$,*2 + 2 CO62+g,*
E2’ G,, = gsl

E2’
G,, =
C+-xd] [(l + cos 2+)g? f @OS2# - cog4)st2
1
(4% = I( 1 - fxXI#Igfi3 -k (CO82gl - cos &‘?
1 -cos# 1
+ (COB4 - cos 2$)gg2 + (eos + - l)gpl]

G = f&l +- 2 co9 2$g=2 + 2 CO8+ga*

G;; = gta + 2 COB2$g,2=
G,, = [0.538/d(2/5)] 2(1 - cos (b)q,$
G,, = [~*0~3~~~2~5)12(1 + ~0s W)q,lt
Gap = [0.538~~~2~5~][2(1 - cos #,g,2a + P(cos 24 - cos+)gr3~f
G,, = [~(2~5)~(1.023)(1 + 00s 2$)1[g,‘, -I- ~0824,1, + ~0s#s,2, i ~0s+g:z
t- cos 2+gt2(J
G,@ = [0.538/( 1.023)(1 t_ cos 2+)][
-(oos Q; - l)tgz@]
-f
1 - co8 #j&p 4 (cos 2$ - 60s #)g~z~

+ = 72”. Expressions for the g’s am given by FATELEY.

(3) The force constants for the CC fundamentals a%greereasonably well among
the 3 ring systems indioat~ng that the CC linkage in ferrocene c~c~opentadieny~
rings is of aromatic nature.

327
 ELLIS R. LIPPINCOTTand RICHARD D. NELSON

(4) The .F,,(C,H,) force constant does not agree well with those of C,H, and
(C,Hz) for species A”,. The fundamental mode associated with this force constant
is a CH bending (I), wa and og. It is to be noted also, that the frequency due to
this mode is considerably higher than in C,H, or (C,H,)+. These differences might
be explained by a pertubation of this mode of vibration due to the ring-metal bond
in ferrocene.
Table 12. Calculated G elements for D,, C,H, ring

Species I Calculated G elements

4’ G,, = 1.0747
G,, = 0.1151
G,, = -0.09788

A," G,,, = 0.9219 x 1016

El’ G,, = 1.0747

G,, = 0.1506
GBP = 1.059 x 1016
G,, = -0.0792
GsP = 0.0458 x lo*
GtB = -0.1605 x l@

El" G,, = 1.150 x 1016

-%’ G,, = 1.0747

G,, = 0.2082
Gax = 0.3787 x 10’6
GOB = 0.9464 x 1016
G,, = -0.0302
G,Ta = 0.1625 x lo8
GsB = 0.0288 x lo8
Gt, = -0.1265 x lo*
GtB = -0.1393 x 10s
Gas = 0.1005 x 1016
-

(5) The valence force symmetry constants of (C,H,) generally compare quite
well with those of C,H, and (C,H,+) indicating that the (C,H,) ferrocene ring is
planar and aromatic.
Recalculated thermodynamic functions
Since the thermodynamic functions were published several of the frequency
assignments have been changed [2]. New calculations were made at 29% 16°K.
The recalculated values do not differ significantly from the original values.
The AH$, reported previously was 57.5 kcal/mole for ferrocene and
79.6 kcal/mole for nickelocene. The latter value is in error and should be
85.9 kcal/mole.
References
[l] LIPPINCOTTE. R. and NELSON R. D. J. Chem. Phys. 1953 21 1307-308.
[2] LIPPINCOTT E. R. and NELSON R. D. J. Amer. Chem. Sot. 1955 ‘?? 4990-4993.

328
 The vibrational spectra and structure of ferrocene and ruthenocene

[3] KEALY T. J. and PAUSON P. L. Nature, Lond. 1951 168 1039-1040.

[4] SIDGWICK N. V. Chemical Elements and Their Compounds. Clarendon Press, Oxford 1950.
[5] LIPPINCOTT E. R. and O’REILLP E. J. J. Chem. Phys. 1955 23 238-244.
[6] KAPLAN L., KESTER W. L. and KATZ J. J. J. Amer. Chem. Sot. 1952 74 5531-5532.
[7] WILKINSON G. J. Amer. Chem. Sot. 1952 '74 6146-6147.
[S] WILKIP*‘SON G., PAUSOPI’ P. L. and COTTON F. A. J. Amer. Chem. Sot. 1954 76 1970-1974.
[9] KING F. T. and LIPPINCOTT E. R. J. Opt. Sot. Amer. 1956 46 661.
[lo] FISHER R. D. Raman Spectra of Certain Colored Substunces and the Existence of an Optimum
Concentration for Maximum Intensity of Scattered Radiation. Unpublished M.S. thesis,
Kansas State College, Manhattan, Kansas 1954.
[ll] HERZBERG 0. Infrared and Ramun Spectra of Polyatomic Molecules. Van Nostrand,
New York 1945.
[12] YOUNG C. W., DUVALL R. B. and WRIGHT N. Analyt. Chem. 1951 23 709-714.
[13] DUNITZ J. D. and ORGEL L. E. J. Chem. Phys. 1955 23 954.
[14] MOFFITT W. J. Amer. Chem. Sot. 1954 76 3386.
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