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LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

Coordination Complexes as Catalysts: The Oxidation of Anthracene by


Hydrogen Peroxide in the Presence of VO(acac)2
Kimberly D. M. Charleton and Ernest M. Prokopchuk*
Department of Chemistry, The University of Winnipeg, Winnipeg MB, Canada, R3B 2E9

bS Supporting Information
ABSTRACT: A laboratory experiment aimed at students who are
studying coordination chemistry of transition-metal complexes is
described. A simple vanadyl acetylacetonate complex can be used as a
catalyst in the hydrogen peroxide oxidation of anthracene to produce
anthraquinone. The reaction can be performed under a variety of
reaction conditions, ideally by dierent students in the same class,
allowing for the accumulation of data that can be interpreted by students in their discussion of the reaction. Performed in the absence
of the vanadium complex, the reaction does not produce any product.
KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Laboratory Instruction, Collaborative/Cooperative Learning,
Hands-On Learning/Manipulatives, Aromatic Compounds, Catalysis, Coordination Compounds, IR Spectroscopy, Thin Layer
Chromatography

ndergraduate chemistry students are familiar with catalyzed


reactions, typically involving either an acid or base as a
catalyst, from introductory organic chemistry courses. In inorganic chemistry courses, these students gain experience synthesizing various metal complexes, but often the product is the end
point with little indication of the signicance, if any, of the
product. Many students are unaware that some coordination
complexes can be used as catalysts in chemical reactions. This
experiment was designed to demonstrate the use of a coordination complex as a catalyst and to introduce the students to
assessing the performance of a catalyst, specically relating
reaction conditions to product yield, percent conversion, and
turnover number (TON).
We chose an oxidation reaction that could be done using
standard glassware without needing any special apparatus to deal
with air or moisture sensitivity. Furthermore, to enhance the
impact of the experiment on the student, we chose an aromatic
substrate, anthracene, for the oxidation (Scheme 1) because
most students are familiar with the concept that aromatic rings
are often resistant to many reactions. The catalyst in this
oxidation reaction was VO(acac)2, which can either be purchased
or synthesized easily.1
In the rst 3-h lab period, all students prepared the catalyst
(Scheme 1). After the synthesis of the catalyst was complete, a
class discussion to determine the various reaction conditions for
the oxidation of anthracene was conducted. In the second lab
period, the students used the catalyst to oxidize anthracene. The
oxidation procedure was based on work reported by Menshikov
and co-workers,2 but the reaction time was reduced so that the
oxidation and separation could be completed in a 3-h period. To
investigate the activity of VO(acac)2 as a catalyst for oxidation,
students used dierent reaction conditions determined in the
class discussion during the rst week. The individual data
generated from the catalysis reactions were shared by the entire
Copyright r 2011 American Chemical Society and
Division of Chemical Education, Inc.

Scheme 1. Catalytic Oxidation of Anthracene

Scheme 2. Preparation of the Catalyst

class. While the reaction was reuxing, the students examined the
catalyst in dierent solvents. A portion of the third lab period was
required for purifying the oxidation products and recording
yields.3

EXPERIMENTAL DETAILS
The preparation of VO(acac)2 was based on a known
procedure1 and modied to use VOSO4 as the starting material
(Scheme 2). The synthesis involved dissolving VOSO4 in water,
adding 2,4-pentanedione, and then adding an appropriate base.
We used saturated Na2CO3 solution and students continued to
add this solution until there was no eervescence upon further
addition. The solid product was ltered o and washed with
water. The solid was allowed to dry on the lter before being
Published: May 20, 2011
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dx.doi.org/10.1021/ed100843a | J. Chem. Educ. 2011, 88, 11551157

Journal of Chemical Education


collected and stored in a sealed sample vial. The product was
characterized by infrared (IR) spectroscopy.
For the oxidation reactions, VO(acac)2 and anthracene were
placed in a round-bottom ask and dissolved in ethyl acetate
(Scheme 1). To this was added hydrogen peroxide and the
reaction was allowed to proceed at the desired temperature for 2
h. When the reaction was done, water was added and the organic
layer removed. The water layer was then extracted with chloroform or dichloromethane and the organic solution was combined
with the ethyl acetate. The organic solvents were evaporated to
isolate the solid product, which was then washed with toluene
and allowed to dry. The product was collected, weighed, and then
analyzed by thin-layer chromatography (TLC) using standard
samples of anthracene and anthraquinone, running three spots
side by side on the same plate. An ultraviolet (UV) lamp was used
to visualize the spots on the TLC plate. If the product was not
pure, further washings with toluene were performed until the
TLC showed pure product.
The capacity for the 5-coordinate structure to accommodate an
additional ligand can be demonstrated by dissolving the compound in coordinating solvents such as pyridine or solutions
containing aqueous ammonia or sodium carbonate. Coordination
of a sixth ligand changes the color compared to solutions in
noncoordinating solvents such as chloroform or dichloromethane.
Given the workup that we use, the catalyst is not easily
collected and recycled.

HAZARDS
All chemicals used in this experiment should be handled with
appropriate care. They are all considered to be irritants and
contact with skin and eyes, and inhalation should be avoided. The
organic compounds are ammable. In addition, chloroform and
dichloromethane are considered possible carcinogens. Hydrogen
peroxide is corrosive and may cause burns, as well as being a
strong oxidizer, which may cause re if brought into contact with
ammable materials. Anthracene is a strong irritant and classied
as an A1 carcinogen.
RESULTS AND DISCUSSION
The synthesis of VO(acac)2 is straightforward. As the students
add the carbonate solution, the evolution of CO2 is a useful
indication that the deprotonation is occurring. When the addition of more carbonate solution does not produce any further
eervescence, the deprotonation is complete. Other bases such
as sodium acetate could have been used at this stage but
carbonate was chosen to expose the students to a dierent
method of determining when the appropriate amount of based
had been added. There is potential for excess carbonate, or
perhaps hydroxide formed due to the presence of carbonate, to
coordinate to the vanadium and decrease the yield of product.
During the addition of base, the product precipitates out of
solution and in the end the mixture is a thick suspension that is
ltered to isolate the product. After washing with water and
allowing the product to dry, a blue-green solid is collected.
Characterization by IR spectroscopy allows for the observation
of the strong VdO peak at 995 cm 1.
No special storage arrangements are necessary if the complex
will be used within the span of a week. If it will be stored for
several weeks or months, then the sample should be kept in a
sealed container to avoid discoloration of the compound. No
other precautions against air or moisture are required. In practice,

LABORATORY EXPERIMENT

Table 1. Typical Results from Instructor and Student Experiments for the Oxidation of Anthracene to Anthraquinone
Average Yield
Conditions
Normala
Half H2O2

Average TON

Anthraquinone (%)

12 ( 0.5
14 ( 2

40 ( 1
50 ( 1

Double catalyst

9(1

60 ( 2

55 C

3.5 ( 1

12 ( 2

40 C

1 ( 0.5

3 ( 0.5

1h

5 ( 0.5

17 ( 1

4h

22 ( 3

73 ( 5

No Catalyst

No H2O2
Double catalyst at 40 C

0
0

0
0

Half everything

6(1

16 ( 1

7.5 mL H2O2, 300 mg

10 ( 0.5

53 ( 1

anthracene, 25 mg catalyst,
and 10 mL ethyl acetate
a

Normal conditions are 500 mg anthracene, 25 mg catalyst, 20 mL ethyl


acetate, 15 mL hydrogen peroxide at reux for 2 h.

this discoloration has not been observed in our teaching labs and
its aect on the reaction has not been investigated.
In addition to the oxidation reaction, it is possible to use
VO(acac)2 for a series of qualitative tests to demonstrate
the eect of coordination of other ligands at the vacant site in
the square pyramid structure. This can also be used to illustrate
the dierence between coordinating and noncoordinating solvents.
For example, in chloroform or dichloromethane, the complex
formed a green solution, whereas in a coordinating solvent, such
as pyridine, the complex forms a yellow-brown solution. Similarly, students can observe how coordination aects solubility
because the complex is insoluble in water whereas it dissolves in
aqueous ammonia.
Using standard laboratory glassware, the oxidation reactions
are performed under a variety of reaction conditions. Some
possible variations include using dierent amounts of catalyst,
anthracene, or peroxide, and using dierent reaction temperatures. After 2 h, the reaction was diluted with water and the
organic layer removed. The aqueous layer was then extracted
with dichloromethane. The organic solutions were combined
and the solvent removed by rotovap. In the absence of a rotovap,
alternative techniques for evaporating the solvent may be used.
Purifying the product is easily achieved by washing with
toluene, which dissolves anthracene but does not dissolve any
signicant quantity of anthraquinone. Our experience has been
that there is always some anthracene present, so to save time and
reduce handling losses, we have the students wash their product
once with toluene before they perform the rst TLC. Although
we decided to use TLC on silica gel to detect when the product
was pure anthraquinone, many instrumental techniques could be
used to quantitatively determine the composition of the reaction
product, which would allow for the percent conversion of
anthracene to be determined. From the TLC, it was easy to
determine if there was still anthracene present in the product,
though the quantity is unknown. If anthracene was present, the
product was washed again with toluene and the sample was again
analyzed by TLC. This procedure was repeated until the product
was pure anthraquinone, which typically took no more than two
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Journal of Chemical Education

LABORATORY EXPERIMENT

washings. Because running the TLC consumes a small amount of


product, it was important to weigh the washed compound before
taking a sample for TLC.
To compare the results of the dierent reaction conditions,
turnover numbers (TON) were calculated to determine the
number of moles of anthraquinone that were produced by each
mole of catalyst. With this common benchmark, students could
compare the eect of temperature and reactant ratios on the
outcome of the reaction. Reactions performed without VO(acac)2 or without H2O2 did not produce any of the anthraquinone product whereas the other reactions produce varying
amounts of anthraquinone. A TON around 14 with a yield of
anthraquinone around 50% can be achieved with 25 mg of
catalyst, 7.5 mL of 30% H2O2, and 500 mg of anthracene at
reux (77 C). Yield and TON drop o dramatically if the
reaction is performed at lower temperatures. Altering the amount
of peroxide or catalyst relative to the anthracene alters the yield
and TON. For example, doubling the amount of catalyst
increases yield to 60% with a TON around 9. Typical student
results are presented in Table 1. Extending the reaction time
from 2 to 4 h increases the yield of anthraquinone. This suggests
that the catalyst is capable of even higher TON and yields if given
a longer reaction time.

SUMMARY
Performing this experiment allowed students to use a relatively simple coordination complex to catalyze an oxidation
reaction that does not occur in the absence of catalyst. Students
enjoy making the complex and then using it to accomplish
another chemical transformation rather than simply making a
complex for its own sake. Students experience not just using a
catalyst to accomplish a desired synthesis, but also study the
catalyst itself and take part in determining the optimum reaction
conditions, much as they would if they were beginning to study a
newly discovered catalyst. Given the quantity of data generated
across the entire class, students also have an opportunity to
develop an in-depth discussion of the reaction.
ASSOCIATED CONTENT

bS

Supporting Information
Student handout; instructor notes; detailed hazards. This
material is available via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author

*E-mail: e.prokopchuk@uwinnipeg.ca.

REFERENCES
(1) Morley, C. P. Inorganic Experiments, 2nd ed.; Wiley-VCH:
Weinheim, 2003; pp 146 148.
(2) Menshikov, S. Y.; Vurasko, A. V.; Petrov, L. A.; Molochnikov,
L. S.; Novoseiova, A. A.; Skryabina, Z. E.; Saloutin, V. I. Russ. Chem. Bull.
1992, 41, 619622.
(3) This experiment can be completed in one 6-h lab period if the
time is well planned and the students are not waiting for chemicals or
equipment, such as the rotovap.
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dx.doi.org/10.1021/ed100843a |J. Chem. Educ. 2011, 88, 11551157