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CHEMISTRY DEPARTMENT

CHT 202: INORGANIC CHEMISTRY (I) PRACTICALS

Student Name
BHEBE NKWANELE
B1441641
. Course Code: CH202

Reg. No.

Course Description INORGANIC CHEMISTRY II


Practical No: 2B
Practical Title: Preparation of a vanadium (IV) complex with acetyl acetone (2.4pentanedione)
Partner(s): MUBVIGWI SITHABILE
Bhebhe Viola

NdlovuSilibaziso

B1441653

B1441603

B1441751

AIM(S)
To synthesise a (VO)2+ Complex ( acetylacetonate complex,)

OBJEVTIVE(S)
To investigate cytotoxic activities of VO2+ complexes against human
cancer cells,by studying literature of VO2+ complexes
To prepare vanadium acetoacetonate by deprotonating a mixture of
tautomer keto and enol to form acetylacetonate anion (acac)
To encourage even boiling,by using boiling chips placed in the flask
with the mixture during refluxing
To observe, record and interpret empirical observations
To calculate the % yield of [VO(acac)2]

Introduction
Oxovanadium complexes exhibit cytotoxic activities against human cancer
cell lines. These chemicals are able to kill target cancer cells at low
micromolar concentrations [1]. Current literature suggests that the therapeutic
characteristics of these metal complexes are influenced by the identity of the
five membered bidentate ligands, as well as the nature of the substituents
on the heterocyclic ring.
Acetyl acetone (2, 4-pentanedione) is a -dike tone. The carbon atom of the
CH2 group in between the 2 carbonyl group is -carbon and the hydrogens
attached to it are acidic. This is due to the presence of 2 electron
withdrawing carbonyl groups. The -hydrogen may be easily lost to water to
produce an anion stabilised by resonance.
The acetylacetonate anion can then act as a ligand towards the oxovanadium
cation to produce VO (acac) 2. This ligand bonds to the metal ion through
both its oxygen atoms and, hence, a six membered, weakly aromatic ring is
produced.

In this experiment, an oxovanadium complex vanadium acetoacetonate VO


(acac) 2 was prepared.

Acetylacetone (2,4-pentanedione) is an organic compound, a -diketone, that exists as


an equilibrium
mixture of tautomeric keto and enol forms. In basic solution, it is deprotonated to form
the
acetylacetonate anion (acac)

APPARATUS/EQUIPMENT
round-bottom flask, 250ml conical flask, 500 ml conical flask,
concentrated H2SO4 , of ethanol, vanadium pentoxide, V2O5 , hydrated
Na2CO3

Procedure
10.0 ml of distilled water was added to a 50 ml round-bottom flask, followed
by the careful addition of an equal volume of concentrated H2SO4.
Then, 25.0 ml of ethanol and 5 g of vanadium pentoxide, V2O5, was added to
the round-bottom flask. The flask was thereafter connected a water cooled
vertical condenser and refluxed vigorously in a heating mantle at a setting of
10 for an hour. The mixture was swirled every 5 minutes. The orange V2O5
solid dissolves in the colourless solvent to produce a dark blue-green
solution.
After an hour, the mixture was cooled in water and filtered using vacuum
filtration. The solid residue was discarded. The filtrate was poured into a
250ml conical flask. 13 ml of acetylacetone was added drop wise to the
filtrate with shaking. The mixture was then neutralised by adding it carefully
to a solution of 20 g of hydrated Na2CO3 in 125 ml deionised water, contained
in a 500 ml conical flask, while swirling the flask.
The resulting mixture was cooled in an ice water bath, before it was filtered
at the pump. The dark green product was washed with cold deionised water
and thereafter, sucked dry by the vacuum pump. The dried product was then
weighed and the percentage yield, determined.
Results and calculation
Empirical observations

V2O5: orange solid


VO (acac) 2: dark blue-green solid
Formation of VO (acac)2
Refluxing V2O5 with concentrated H2SO4, water and ethanol for an hour,
reduces V2O5 to (VO)2+, as described in the equation below. Orange V2O5
dissolves in the colourless solvents to form a dark green (VO)2+ solution.
V2O5 + 4H+ -> 2(VO)2+ + 2H2O + 1/2O2
The vanadium (II) ion was chelated with 2 acac anions to form blue-green
[VO(acac)2]. This complex has a square-based pyramidal geometry and is
able to accommodate one more ligand.

(VO)2+ + 2 acacH -> 2H+ + VO (acac)2


Na2CO3 was added in order to remove the excess H+ from the ionisation of
acacH and concentrated H2SO4 so as to drive the reaction to completion. By
Le Chateliers principle, with the removal of H+ ions, the equilibrium of the
reaction is shifted to favour the formation of the VO(acac)2 complex.

Preparation of VO (acac) 2

Weight of V2O5 used:


Mass of beaker/g
Mass of beaker +
V2O5/g
Mass of V2O5/g

2.00 g

1
37,013
39,013

2
37,013
39,013

3
37,013
39,013

2,00

2,00

2,00

Weight of hydrated Na2CO3: 20 g


Mass of beaker/g
Mass of beaker +
Na2CO3/g
Mass of Na2CO3 /g

1
37,013
57,013

2
37,013
57,013

3
37,013
57,013

20,00

20,00

20,00

1
1,0561

2
1,0561

3
1,0561

5,4661

5,4661

5,4661

4.41

4,41

4,41

Weight of dried VO (acac) 2:

4,41g

Mass of product=4,41g

Mass of filter
paper/g
Mass of paper +
product/g
Mass of product/g
V2O5 + 4H+

2(VO) 2+ + 2H2O + 1/2O2

(VO)2+ + 2 acacH

2H+ + VO (acac)2

(1)
(2)

No. of moles of V2O5 used = 2.00 / (50.94 x 2 + 5 x 16.00) = 0.01099 mol


Using equation 1 and 2, each mole of V 2O5 yields 2 moles of (VO)2+ and
hence 2 moles of VO (acac)2.
No. of mole of VO (acac)2 = 0.010996 mol 2 = 0.02199 mol
Mr of VO(acac)2 = (50.94 + 16.00) + 2(5 12.01 + 7 1.008 + 2
16.00) = 265.15 g mol-1
Theoretical yield of VO(acac)2 = (265.15 g/mol) 0.021992 mol = 5.831 g

Percentage yield of VO (acac)2 = 4.41 / 5.831 x 100% 75.6 %

Mr of VO(acac)2py = 265.16 + 5 12.01 + 5 1.008 + 14.01 = 344.26 g


mol-1

Infrared Spectra of VO(acac)2


From theory

Spectrum obtained,
VO(acac)2py
V=O
stretching

965.3 cm-1

Sample spectrum, VO
(acac)2
997 cm-1

Amount by which the band shifted = 997 965.3 = 31.7 cm-1


Colours of products
V2O5, VO (acac)2 and VO(acac)2py are coloured because they absorb light in
the visible region. The energy of the absorbed photon corresponds to the
energy gap between vanadium ions d-orbitals. The colour of the compound
observed is complementary to that of the absorbed light.
Percentage yield of products
The percentage yield of the product, VO(acac)2, was a reasonable 75.6%.
However, it was not 100%. This may be due to improper mixing of the
reagents within the round bottom flask which resulted in lesser amount of
V2O5 reacting to produce lesser VO2+ which is subsequently required to
form VO(acac)2. The yield could be increased by refluxing the mixture longer
and ensuring more thorough swirling to allow more conversion of V2O5 to

VO(acac)2. More time is required to leave the mixture to stand in an ice bath
for crystallisation after Na2CO3 is added in order to produce a higher yield of
VO(acac)2. More base may be added to favour the formation of the desired
product as well.
Precautions
As the reagents may be toxic, gloves were worn to protect the hands. This is
especially important when handling corrosive reagents such as concentrated
sulphuric acid. The experiment was carried out in the fumehood to prevent
any inhalation of harmful organic vapours. The flammable reagents
acetylacetone) were also placed away from naked flames.
Also, the solution of (VO)2+ was not filtered with cotton wool, which was
suggested by the lab schedule. Instead, filter papers were used. This was
because cotton wool may be easily dislodged and thus, allow unreacted V 2O5
to pass through. By contrast, filter paper is more effective at separating the
insoluble unreacted reagent and soluble product[4] .

Conclusion
The preparation and chemical analysis of oxovanadium acetylacetonate,
allow the chemical properties of the product to be characterised. The
percentage yield of VO(acac)2.
(i)

The formula of the product is VO ( acac)2. Name and draw the structure of
the Complex.
(VO)2+ + 2CH3COCH2COCH3

2 H+ + VO(CH3COCHCOCH3)2

C10H16O5V Vanadium(V)-oxyacetylacetonate
Structure of the complex

(ii)

Record the yield and calculate the percentage yield of the reaction.
Percentage yield of VO (acac)2 = 4.41 / 5.831 x 100% 75.6 %

(iii)

How would you expect the compound to react with pyridine? Give the
structure
Of the expected product.
Pyridine has a lone pair of electrons on the N atom which can be used to bind
with the central vanadium ion to form a 6-coordinated complex. The overall
structure of the grey complex, VO(acac)2py, will be octahedral
VO(acac)2 + py

VO(acac)2py

References

Glidewell, C. Metal Acetylacetonate Complexes: Preparation and Characterisation.


In Inorganic Experiments, Third Edition; Woolins, D., Ed.; Wiley-VCH: Weinheim,
Germany, 2010; pp 109-119.
2) Evans, D. F. The Determination of the Paramagnetic Susceptibility of
Substances in Solution by Nuclear Magnetic Resonance. Proc. Chem. Soc. 1959,
2003-2005.
3) Grant, D. H. Paramagnetic Susceptibility by NMR: The Solvent Correction
Reexamined. J. Chem. Ed. 1995, 39-40.
4) Schubert, E. M. Utilizing the Evans Method with a Superconducting NMR
Spectrometer in the Undergraduate Laboratory. J. Chem. Ed. 1992, 69 (1), 62.
5) Greenaway, A. M.; Trail, L. E. Magnetic Susceptibility: A Practical Introduction.
J. Chem. Ed. 1983, 8, 681-682
.
6) Seco, M. Acetylacetone: A Versatile Ligand. J. Chem. Ed. 1989, 9, 779-780.