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Cyclopentadiene
Wilkinson, Rosenblum, Whitting and Woodward soon corrected this view of Ferrocene's
structure and proposed the currently accepted "picture"of its bonding:
First to the bonding in the ligand; Cyclopentadienyl Anion. Because of the resonance
stabilization of its anion, Cyclopentadiene is unusually acidic:
C5H6
C5H5- + H+
or
Group theory can then be employed (cf. Cotton) to determine how these MOs interact with the
orbitals of the valence shell of the Fe2+ atom to give MOs of the entire molecule with the correct
molecular symmetry, D5d. For example, the interaction of the dyz orbital of the metal with E1
MOs of the rings is as pictured.
Based on this type of analysis, a crude MO diagram for Ferrocene can be constructed. (See
figure on next page.) Note that Ferrocene is an extremely stable complex, stable in Air to
temperatures of 500oC, because its 18 valence electrons occupy only bonding and non-bonding
MOs. Twelve of these electrons are contributed to the structure by the cyclopentadienyl rings
and occupy the lowest six Ferrocene MOs. The six electrons of the Fe2+ contribute to the
Ferrocene metal-like MOs. The strictly anti-bonding MOs of Ferrocene are not occupied.
(C5H5)2Fe
A strong base such as Potassium Hydroxide, KOH, will react with the acidic Cyclopentadiene to
produce the needed Cyclopentadienyl Anion:
C5H6 + OH-
C5H5- + H2O
Our source of Fe2+ will be Ferrous Chloride Tetrahydrate; FeCl24H2O. Overall, the synthetic
reaction is:
8 KOH + 2 C5H6 + FeCl24H2O
This reaction requires a solvent which is sufficiently polar to allow for the dissociation of the
Potassium Hydroxide and yet allow for solvation of the hydrocarbon. Two solvents suitable for
these purposes are Glyme (1,2-dimethoxyethane) and DMSO (dimethylsulfoxide). Additionally,
the solvent must allow for the removal of the Water produced when the proton is abstracted from
Cyclopentadiene otherwise the Iron will be oxidized to Fe3+. Glyme and DMSO both allow for
the complexation of excess KOH with Water, effectively "removing" the latter from the reaction
mixture.
Finally, because of the aromatic nature of the Cyclopentadienyl rings, the Ferrocene compound
exhibits chemistry similar to Benzene. In fact, it is this chemistry which provides an important
clue as to the nature of the Cyclopentadienyl ligand in the compound.
In 1877, Charles Friedel and James Crafts discovered that an acyl halide reacts with
Benzene in the presence of an aluminum halide AlX3 (X = Cl, Br). The products of this
reaction are the corresponding acylbenzene and hydrogen halide (HCl or HBr). This
reaction, which can be carried out in the presence of other Lewis acids catalysts, is called
the Friedel-Crafts Acylation reaction.
Thus, in this exercise we will synthesize and purify Ferrocene. This compound will then be
acetylated using a Friedel-Crafts Acylation to demonstrate the aromatic character of its ligands.
Procedure
Cracking Dicyclopentadiene
Cyclopentadiene, is obtained from a light oil derived from coal tar distillation. Because
Cyclopentadiene is such a reactive system, at Room Temperature it exists as a stable
dimer, Dicyclopentadiene. This is a Diels-Alder adduct of two molecules of the diene.
Thus, generation of Cyclopentadiene involves heating the dimer to initiate a "retro-" or
"reverse-Diels-Alder" reaction.
2.
Heat the dimer with a heating mantle until it refluxes briskly and at a rate such that
the monmeric diene begins to distill in about 5 minutes and soon reaches a steady
boiling between 40oC and 42oC. Do not exceed the boiling point of 42oC.
Synthesis of Ferrocene
1.
Grind 0.750g of KOH in a Mortar as rapidly as possible. Wear gloves and work in a
fume hood while performing this operation.
2.
3.
Cap the flask with a good septum and pass nitrogen into the flask and through the solution
for about 1 minute.
4.
Begin stirring the mixture so that as much of the solid as possible dissolves.
5.
To a 10 mL Reaction Tube add 0.350g of finely powdered Iron (II) Chloride Tetrahydrate
and 1.5 mL of DMSO (Dimethyl Sulfoxide).
6.
Cap the tube with a good rubber septum and pass nitrogen into the tube for about 1 minute.
Now shake the tube vigorously until all the Iron Chloride dissolves. Some warming may
be needed.
7.
Using an accurate syringe, add 0.30 mL of freshly distilled cyclopentadiene directly to the
mixture of KOH in Glyme. Do not grasp the body of the syringe, because the heat of your
hand will cause the cyclopentadiene to volatilize. Stir the flask vigorously. The solution
will turn brown in color because of the formation of potassium cyclopentadienide salt.
8.
After waiting about 5 minutes for the anion to form, pierce the septum with an empty
needle for pressure relief and inject the Iron Chloride solution in six 0.25 mL portions over
a 10 minute period. Stir the mixture well. After all the Iron Chloride has been added, rinse
the reaction tube with 0.25 mL of DMSO and add this to the flask. Continue to stir of
shake for about 15 minutes to complete the reaction.
9.
Prepare a mixture of 5.0g Ice and 4.5 mL of 6M HCl in a graduated xylinder and add this
mixture to a 30 mL beaker. To isolate the Ferrocene, pour the dark reaction slurry into the
beaker with the ice and HCl. Stir the mixture thoroughly to neutralize any remaining KOH.
(Test the mixture with pH paper. If needed, add more HCl.)
10. Filter the orange crystals using a Hirsch funnel. Wash the crystals with two 1 mL portions
of chilled water. Draw air through the Hirsch funnel for 5 minutes. Dry the crystals
between the folds of filter paper. Finally dry the product on a filter paper.
11. Purify the crude product via sublimation.
12. Weight the product.
13. Determine the melting point in a sealed capillary; since the product sublimes.
14.
Acetylation of Ferrocene
1.
Place 0.5 mmole of sublimed Ferrocene in a 5 mL round-bottom flask with a magnetic stir
bar. Add 0.35 mL of Acetic Anhydride using a dry Pastuer pipet. Add 0.1 mL 85%
Phosphoric Acid using a 1 mL syringe. Cap the flask with a septum and push a clean
needle through the septum. This will minimize the amount of moist Air that enters the
flask, and allow for release of any gas evolved.
2.
Dissolve the Ferrocene by gently heating the flask on a heating the flask on a sand bath
while carefully stirring and agitating the flask.
3.
Continue heating for an additional 10 minutes and then place the flask in an ice-bath.
Remove the needle and spetum, and carefully add 0.5 mL of ice-cold Water dropwise with
a thorough mixing.
4.
5.
Filter the mixture by vacuum filtration, rising out the flask and washing the solid collected
with cold water. Remove the solid from the filter and place it on a filter paper. Press the
product as dry as possible between sheets of filter paper.
6.
Separate the crude product via column chromatography. Use Alumina as the packing
material and form your initial slurry using Pet Ether. Apply your solid to the column by
dissolving it in a minimum amount of Dichloromethane, adding 300 mg Alumina, heating
to remove the Dicholormethane and then applying the mixture to the column. Wash the
compound onto the column using a small amount of Pet Ether. Elute the compound with
several small portions of Pet Ether. Elute any Ferrocene with Pet Ether. Then, elute the
Acetyl Ferrocene with a 50:50 mixture of Pet Ether and t-Butanol.
7.
Collect the Acetyl Ferrocene, evaporate the solvent and weigh the product. Determine your
percentage yield.
2.
3.
4.
References
Cotton, F. Albert Chemical Applications of Group Theory Wiley-Iterscience,
New York, 1971.
Huheey, James E.; Keiter, Ellen A. and Keiter, Richard L. Inorganic Chemistry:
Principles of Structure and Reactivity Harper Collins, 1993.
Kealy, T.J. and Pauson, P.L. "A New Type of Organo-Iron Compound" Nature
168 (1951) 1039.
Miessler, Gary L. and Tarr, Donald A. Inorganic Chemistry Prentice Hall,
Boston, 2011.
Miller, Samuel A.; Tebboth, John A. and Tremaine, John F.
"Dicyclopentadienyliron" J. Chem. Soc. (1952) 623.
Purcell, Keith F. and Kotz, John C. An Introduction to Inorganic Chemistry
Saunders College Publishing, Philadelphia, 1980.
Streitwieser, Andrew, Jr. and Heathcock, Clayton H. Introduction to Organic
Chemistry Macmillan Publishing Co., 1981
Wilkinson, Geoffrey; Rosenblum, M.; Whiting, M.C. and Woodward, R.B. "The
Structure of Iron Bis-Cyclopentadienyl" J. Am. Chem. Soc. 74 (1952) 2125.