Investigating the Synthesis and Reactivity of Ferrocene

Norshafiqaliana Zaini

Abstract. In this experiment, 3 major reaction are conducted which are to synthesis and

purify ferrocene via the reaction of the anion of cyclopentadiene with iron (II) chloride

solution, testing the redox reactions for ferrocene and substitution Friedel-Crafts reaction of

ferrocene with acid anhydride to form substituted ferrocene. Column chromatography was

used to separate the product from acetylation reaction because the products are neutral and

have a different polarity. Melting point, NMR and IR spectroscopy can be conducted to

convince the presence of ferrocene, monoacetyl ferrocene and diacetylferrocene from both

reactions. Ferrocene can undergo synthesis reaction and do a redox reaction. The H at

cyclopentadienyl ring in ferrocene can be substitude with acyl group and form the substituted

ferrocene. All of these techniques can be used to analysing ferrocene and its behaviour.

Introduction

Ferrocene was the one of fascinating stories of chemical research and was discovered about

50 years ago. Development of ferrocene chemistry growth a vigorous interest in the chemistry

of organometallic chemistry and brought a new stimuli into coordination chemistry.

Ferrocene is a stable organometallic compound consists of two cyclopentadieny rings bound

on the opposite of a central metal atom, Fe 2+ and also known as dicyclopentadienyliron and

have molecular formulae of (C5H5)2Fe. Ferrocene also called as a sandwich compounds

because such characteristic it had.

The cyclopentadienyl ion is an aromatic because it has a cycle of 5p orbitals containing a total

of 6 electrons hence obeying Huckels rule 4n+2 rule for aromaticity. This structure made

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cyclopentadienyl ion is particularly stable and caused ferrocene behave like benzene and other

aromatic compounds. Thus ferrocene can undergoes substitution reactions such as

halogenations, nitration, Friedel-Crafts alkylations and acylations reaction.

For the synthesis of ferrocene, the uses of strong bases such as potassium hydroxide (KOH)

needed to be considering because cyclopentadiene is relatively acidic among a simple

hydrocarbons with pKa of 15.5. The bases will deprotonate cyclopentadiene to

cyclopentadienyl ion and allowed it react with ferrous ion, Fe2+ to form ferrocene compound.

The suitable solvents, such as 1, 2- dimethoxyethane and dimethyl sulfoxide (DMSO) used to

provide polarity condition to help favour the dissociation of the potassium hydroxide into

hydroxide and potassium ions.

This experiment was divided into 3 sections with their specific aim. The first section is to

synthesise and purify ferrocene under inert atmosphere. The second section is to investigate

the redox behaviour of ferrocene and the last section aims to use Friedel-Crafts acetylation to

make monoacetyl ferrocene and to separate and identify the product(s) by using column

chromatography, 1H NMR and IR spectroscopy.

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Experimental

Synthesis and Purification of Ferrocene

Figure 1: 2 steps reaction for synthesis of ferrocene.

Potassium hydroxide (8.00 g , well crushed) was added to a 1,2- dimethoxyethane (20.0 cm 3)

and mixed well under an inert atmosphere (N2 gas). Cyclopentadiene (1.8 cm3) was added

slowly into a solution against a N2 gas flow and was stirred for 10 minutes. The solution of

FeCl2 (2.03 g, 0.01 mol) in DMSO (8 cm 3) was added into a solution mixture. The reaction

mixture was continuously stirred for 30 minutes after all FeCl 2 solution added. The flow of N2

was stopped and the solution was added into a prepared slurry solution, HCl (30 cm 3, 6

moldm-3 ) and ice (30.0 g) , and was stirred for 15 minutes. The slurry solution was filtered,

washed by using water (4 x 10 cm 3) and air dried. The precipitate obtained which is a crude

ferrocene (0.72 g , 24.2%) was transferred to a watch glass, dried by using steam bath for 5

minutes, and was allowed to cool down for a further 5 minutes. The mass and appearance of

crude ferrocene was recorded. The crude ferrocene was purified by vacuum sublimation

method (silicon oil bath) and the product of sublime was collected, weighed and get its

melting point range, and submitted. The purified ferrocene was obtained as a orange crystals

(0.56 g, 24.2 %) ; mp 162-166 oC, 760 mmHg.

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Redox behaviour of ferrocene

The mixture of acetone (10.0 cm3) and provided ferrocene (0.10 g) was prepared and forming

a yellow- orange colour solution. The solution of water (5 cm3) and iron (III) chloride (0.10 g)

forming a yellow- orange colour solution as well. The solution of iron (II) was added into a

half of solution of ferrocene and dark blue colour solution was obtained. The dark blue

solution was then added with a small spatula of ascorbic acid following by addition of

dichloromethane until a discernable layer was formed. The mixture then was shook well and

yellow colour solution was obtained as it is a top layer of solution. This top layer was

suspected to be a ferrocene and was confirmed by adding some iron (II) solution and top layer

turns into dark blue solution. The remainder of ferrocene solution was then added with a few

drops of provided silver nitrate and was left for 5 minutes. The solution was changed from

yellow-orange to dark blue solution.

Acetylation of ferrocene

Figure 2: Reaction of acetylation of ferrocene

A solution of ferrocene (0.25 g, 1.34 mmol) and acetic anhydride (5 cm 3, 1.08 gcm-3) was

prepared and added with a orthophosphoric acid (0.25 cm3, 85%), dropwisely with constant

stirring. The mixture was protected with a freshly made CaCl2 tube and heated with a boiling

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water bath for 10 minutes. It was then cooled in ice bath and ice water (1.0 cm 3) was added

dropwisely followed by addition of ice (10.0 g). Sodium hydroxide (22 cm 3, 4 mol dm-3) was

added into a reaction mixture dropwisely and tested with a ph paper until the mixture became

neutral. The reaction mixture was then extracted with ethyl acetate (2 x 10 cm3) and the

organic and aqueous layer was separated thoroughly. The organic layer was washed with

water (20 cm3), dried (MgSO4), filtered by gravity filtration and undergoes rotary evaporation.

The compound obtained was separated by a column chromatography (silica gel) and the

separated product obtained was later identified by using thin layer chromatography analysis,

IR and 1H NMR spectroscopy. The acetylated ferrocene compounds obtained was a

monoacetyl ferrocene and appear as dark yellow solids (0.05 g, 0.23%).

Results and discussion

Synthesis and purification of ferrocene

The synthesised of ferrocene required two-step reaction:

1)
C5H6 + KOH C5H5 + H2O + K+

2)
2C5H5 + FeCl2.4H2O + 2K+ C10H10Fe + 2KCl + 4H2O

Numerous colour changed were observed during the synthesised process of ferrocene. The

formation of potassium salt of cyclopentadiene, Cp after the addition of Cp into KOH and

dichloromethane solution turned the white colour solution into pink colour solution. When

yellowish iron (II) chloride was added into a solution, it turns into a green colour solution.

The product from the filtration process was orange-yellow colour solid which was desired

product ferrocene. A yield of 24.2 % was obtained from the experiment which a very low

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yield. This could be because of an amount of cyclopentadiene and cyclopentadienyl anions

revert back to the dicyclopentadienyl (Diels- Alder reaction cannot be stopped or prevented)

due to slightly high temperature during the experiment. Conversion process can be minimized

by keep the temperature as low as possible. Only cyclopentadiene could have reacted with

iron (II) chloride to form ferrocene. This effectively reduces the amount of ferrocene formed.

Besides that, during the stirrer process, lots of reactant was splash on the wall of flask due to a

vigorously stirred by magnetic stirrer. This effect the amount of reactant reacts to form

ferrocene and low yield of ferrocene was obtained. Vacuum sublimation was conducted to

improve the purity of ferrocene. During sublimation, product was formed at the cold-finger,

forming purified crystals of ferrocene (0.56 g, 18.8 %).

Redox reactions of ferrocene

Reaction with FeCl3:

Ferrocene act as a reducing agent. Fe2+ ion in ferrocene will oxidise to Fe3+.

Equation: [Fe (C5H5)2]2+(aq) [Fe(C5H5)2]3+(aq) + e-

Fe3+ (aq) + e- Fe2+(aq)

Overall equation: [Fe(C5H5)2]2+(aq) + Fe3+(aq)[Fe(C5H5)2]3+(aq) + Fe3+(aq)

Reaction with ascorbic acid:

Ascorbic acid acted as a reducing agent and it reduced Fe3+ to Fe2+ ion.

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Reaction with silver nitrate, AgNO 3:

Ferrocene acted as reducing agent and reduced Ag+ to Ag

Equation: Ag+ + e- Ag(s)

[Fe(C5H5)2]2+(aq) [Fe(C5H5)2]3+(aq) + e-

Overall equation: [Fe(C5H5)2]2+(aq) + Ag+ (aq) Ag(s) + [Fe(C5H5)2]3+(aq)

As a conclusion, the entire redox test showed that ferrocene is a good reducing agent while

the reactants are a good oxidising agent.

Acetylation of ferrocene

Depending upon the reaction condition, either monoacetylferrocene or diacetylferrocene were

the major products of acylation. For this experiment, only monoacetylferrocene was obtained

as the milder reactions condition (water bath was not really boiling during the reaction) was

used.

The solvent for the reaction mixture was 70:30 ratio of 40-60 petroleum ether: ethyl acetate as

this combination gives the best separation (R f = 0.67). The Rf value calculated using formula

as followed.

Rf = Distance travelled by compound / distance travelled by solvent

As the compounds are neutral, column chromatography method (adsorption) was used to

separate the mixture of ferrocene and acetyl ferrocene. Separation started by using a non-

polar eluent (100% 40-60 petroleum ether) in order to bring down the entire non-polar

ferrocene compound. As the non-polar ferrocene moved with non-polar petroleum ether

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through the silica gel adsorbent, a yellow band was observed moving down the column. The

acetyl ferrocene was left behind as it is more polar than a ferrocene. By gradually increased

the polarity of eluent with the addition of ethyl acetate in solvent mixtures, acetyl ferrocene

can be observed moving down the column as a dark yellow band. All of these observations

showed that polarity is the most important factor in separating the neutral compound.

Despite all of the interesting observations mentioned, only a small amount of monoacetyl

ferrocene were obtained after the rotary evaporation which just enough to make the 1H NMR

analysis; chemical shifts in ppm, 2.40 (3H), 4.23 (5H), 4.60 (2H), 4.80 (2H). For the melting

point, the ideal value for monoacetyl ferrocene is 81 83 oC. There will be a peak at 1670-

1820 cm-1 which C=O stretching for IR spectroscopy of an ideal monoacetyl ferrocene.

Conclusions

As stated in the introduction, the aims of this experiment including to synthesis and purify

ferrocene, to investigate the redox behaviour of ferrocene, to attempt a Friedel- Crafts

acetylation of ferrocene, as well to separate and identify the products by column

chromatography. All the aims were successfully achieved in the period given.

In terms of yield, both of synthesis and acetylation of ferrocene gives a low yield which

affected the analysis of the formed products. The improvement on the experimental

techniques should be done to increase the yield of products. For example, the acetyl ferrocene

should not be heating for a long time and the water bath need to be boiling during the

reaction. In addition, the column chromatography also should not being done in a one day as

the eluents easily evaporated and affects the mobile phase inside the column resulting in

improper separation of products.

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References

1. Catherine E. Housecroft and Alan G. Sharpe, Inorganic Chemistry, Pearson Education

Limited, 2005, 2nd ed. , pp. 731- 733.

2. J. Clayden, N. Greeves, S. Warren and P. Wothers, Organic Chemistry, Oxford, 2004,

1st ed., pp. 573, 622

3. Lab assistant

Appendices

Yield calculation for the synthesised and purified ferrocene

Compound Mass used/ Molar mass (g Moles (mol)

obtained (g) mol-1)

FeCl2. 4H2O 2.03 126.711 0.01602
Crude ferrocene 0.72 186.04 0.00387
Sublimed ferocene 0.56 186.04 0.00301

Percentage yield of:

Crude ferrocene = (0.00387/0.01602) x 100% = 24.2%

Sublimed ferrocene = (0.00301/0.01602) x 100% = 18.8 %

Yield calculation for acetylation of ferrocene

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Compound Mass used/ Molar mass (g Moles (mol)

obtained (g) mol-1)

Ferrocene 0.25 186.04 0.134400
Monoacetyl ferrocene 0.07 228.07 0.000307

Percentage yield of product:

Yield = (0.000307/0.134400) x 100% = 0.23%

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