Purification of Ferrocene by Sublimation: Comparing Crude

Ferrocene and Pure Ferrocene Using HNMR, CNMR, IR and UV-

Vis

Steven O’Rourke, Brandon Carson and John Dilyard

Department of Chemistry, University of Akron

Received October 9, 2017

Crude bis-(cyclopentadienyl)Iron(II), more commonly referred to as ferrocene, (C5H5)2Fe, is

easily purified through sublimation and recrystallization into Pure Ferrocene. The reason

sublimation is a quick and easy method to purify ferrocene is that the sublimation point of

ferrocene is below the melting point, which allows the ferrocene to be quickly and easily

sublimed, allowing it then to be recrystallized into its pure form. After finishing the sublimation

and recrystallization process, samples of the crude and pure ferrocene were run through HNMR,

CNMR, two different run methods of IR, as well as UV-Vis. These methods would help to

identify whether the differences, although very slight in some cases, between the crude and pure

ferrocene.

Introduction

Ferrocene was the first sandwich compound discovered in 1951 by Thomas J Kealy and

Peter L. Pauson accidentally when trying to synthesize fulvalene. This discovery would lead to

them winning the Novel Prize in chemistry in 1973. 1 The original synthesis of ferrocene was

done through a simple laboratory method that was illustrated by Kealy and Paulson. 2,3

Ferrocene is now an often used as a polymerization catalyst through various substitutions to the

ring and is also used as anti-knock additives.4

 Ferrocene is an organomettalic complex consisting of an iron atom sandwiched between

two cyclopentadiene rings. Because of this, ferrocene is also referred to as a sandwich compound

or a metallocene.

Ferrocene was one the first organometallic compound discovered and led to the discovery

of many transition metal complexes that have continued to revolutionize the field of chemistry.

The compound is extremely stable when in the presence of water and is soluble in organic

solvents. 1

Results and Discussion

A melting point was taken for both the crude pure ferrocene. The pure ferrocene yielded

a melting point of about 173oC which is lower than the literature value of 174oC5, but still shows

that the compound is still much purer than its crude form which gave a melting point range from

172oC-175oC, this wide range is brought about by the impurities in the crude ferrocene.

To further our assertions that the sublimation and recrystallization of the ferrocene

purified, we also took 1HNMR, 13CNMR, UV-Vis and IR readings of both the pure ferrocene and

crude ferrocene to decipher what effects the impurities in the crude ferrocene had on its various

spectras.

The UV-Vis spectra for Pure Ferrocene (See Figure 1) was extremely similar to that of

the crude ferrocene (See Figure 2). Both recorded an absorption of 0.495-0.499 at a wavelength

of 442.00 nm. These measurements are consistent with the observation that both compounds

were a bright orange color, although the pure ferrocene was a brighter orange, because the crude

ferrocene was 98% ferrocene, the UV-Vis could not differentiate greatly between the crude and

the pure.
 Fig. 1 Fig. 2

The IR spectra for crude ferrocene and pure ferrocene were taken using two separate

methods, the first, dissolving the ferrocene into a solvent and applying the solvent onto the

machine. To further test, the salt plate method for IR was also used to not only learn various

methods of IR but to also guarantee accuracy in the readings. The spectra for pure ferrocene and

crude ferrocene, like the of the UV-Vis absorption, were very similar. The pure ferrocene (Fig. 3

and 4) shows peaks around 3098 cm-1, which are indicative of C-H stretching. The peak at

1651cm-1 is a representation of the C=C bonds and the peak at 746 cm-1 ring torsion in both the

sandwich cyclic pentyl groups.

Fig.3 Fig.4

The crude ferrocene IR spectra showed very similar peaks to that of the pure ferrocene, again

with peaks at 3098 cm-1 indicating the C-H bonds, peak at 1651 cm-1 indicating C=C bonds and a
peak at 739 cm-1 representing the ring torsion. The large difference that shows that this is crude

compared to the pure ferrocene is that there is a large number of peaks below 1500 cm-1 which

are indicative of the interference from the impurities in the crude ferrocene.

Lastly 1HNMR (See Fig. 5 and 7) and 13CNMR (See Fig. 6 and 8) spectra were taken for

both the crude and pure ferrocene. The 1HNMR spectrum for the crude ferrocene, like that with

the IR spectrum, shows where the impurities occur and how the pure ferrocene is experimentally

proven to be purer than the crude ferrocene that was provided. The difference being that in the
1
HNMR spectra for the crude ferrocene showed a resonance at 2.182 ppm which could be a

representation of an Iodine impurity in the crude ferrocene. The 13CNMR for the crude and pure

ferrocene were essentially identical, with the resonances shown for the 13C all at around the same

values.

Conclusion

In conclusion, many compound-identifying methods were used in this experiment to

show that the crude ferrocene was in fact purified through the sublimation and recrystallization

process. Not all the methods, namely UV-Vis, were indicative that the ferrocene had indeed

been purified. Despite that one method that was unable to provide a definitive difference

between the crude and pure ferrocene, the IR spectra and the 1HNMR spectra were able to

explicitly point out the differences between the purified ferrocene and the crude ferrocene as well

as identifying the possible impurity in the crude ferrocene.

Experimental Section

General Procedures. Sublimation and recrystallization were carried out under lab conditions,

using a Fischer Scientific Isotemp hot plate to perform the sublimation. The recrystallization was

finished after carrying out5 collections over 55 minutes. Experiment began with 266.1 mg of
Crude ferrocene which was then sublimed and recrystallized into pure ferrocene which yielded

159.3 mg and a 60% yield in product. The Ferrocene was purchased from Sigma Aldrich

Chemical Company. The 1HNMR and 13CNMR spectra were recorded on a 300 MHz Varian

NMR. The ferrocene was dissolved in CDCl3, which was purchased from Cambridge Isotope

Technologies, to perform the NMR readings. The melting points were taken using an

Electrothermal Mel-Temp. The IR spectra were obtained using a Thermoscientific Nicolet i55

and the product was dissolved in Methylene Chloride, which was purchased from Fisher

Chemical. The UV-Vis spectra were obtained using a Cary 100 Bio UV-Visible

Spectrophotometer and like with the NMR spectra, the UV-Vis spectra were obtained by

dissolving the ferrocene in CDCl3.

Melting Point. Melting point range of pure ferrocene was recorded at 172-173oC. Melting

Point range of crude ferrocene was recorded at 172-175oC.

UV-Vis. Crude Ferrocene recorded an absorbance of 0.499 at 442.00nm. Pure Ferrocene

recorded an absorbance of 0.496 at 442.00nm

Infrared Spectra.

Crude Ferrocene

cm-1 Description

3098 Sharp

3052 Sharp

3052 Sharp

2985 Sharp

1699 Sharp

1651 Sharp
 1418 Impurity

1418 Impurity

1265 Impurity

1106 Impurity

1004 Impurity

739 Sharp

Pure Ferrocene

3098 Sharp

3051 SHARP

2985 Sharp

2916 Sharp

2848 Sharp

1265 Impurity

746 Sharp

1HNMR. Crude Ferrocene. (CDCl3, ppm) 4.17 (t, 8H, C5H4) 2.182 (s, 1H, CHI3) 1.552 (s, 2H,

CH2)

Pure Ferrocene. (CDCL3, ppm) 4.17 (s, 10H, C5H5) 1.545 (s, 1H, CH)
13CNMR Crude Ferrocene (CDCl3, ppm) 77.655 (s, C-Fe) 77.230 (s, C-Fe) 76.805 (s, C-Fe)

68.136 (s, C=C)

Pure Ferrocene (CDCl3, ppm) 77.655 (s, C-Fe) 77.230 (s, C-Fe) 76.805 (s, C-Fe) 68.136 (s,

C=C)
Bibliography

(1) Kauffman, G. J. Chem. Educ. 1983, 60 (3), 185–186.

(2) Rausch, M.; Vogel, M. J. Chem. Educ. 1951, 268–272.

(3) Kealy, Thomas J. Pauson, P. L. Nature 1951, 168, 1039–1040.

(4) Heinze, Katja Lang, H. Organomettalics 2013, 32 (20), 5623–5625.

(5) Clu, K. J.; Blu, J. Organometallics 2016, 35, 3939–3948.