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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
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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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
10 ( 0.5
53 ( 1
anthracene, 25 mg catalyst,
and 10 mL ethyl acetate
a
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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LABORATORY EXPERIMENT
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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