Introduction

Acetylacetone (2,4-pentanedione) is a -diketone. The carbon atom of the CH group in between

2

the 2 carbonyl group is α-carbon and the hydrogens attached to it are acidic. This is due to the
presence of 2 electron withdrawing carbonyl groups. The α-hydrogen may be easily lost to water to
produce an anion stablised by resonance (as shown below):

The acetylacetonate anion can then act as a ligand towards the oxovanadium cation to produce
VO(acac) . This ligand bonds to the metal ion through both its oxygen atoms and, hence, a six
2

membered, weakly aromatic ring is produced (as shown below):

Refluxing with pyridine causes further metal-ligand coordination and produces VO(acac) py. IR
2

spectroscopy is useful then in distinguishing between the vibrational energies of the dark blue-
green VO(acac) and greyish VO(acac) py.
2 2
Results and calculation

Empirical observations

V O : orange solid
2 5

VO(acac) : dark blue-green solid

2

VO(acac) py: greenish grey solid

2

CuCl2 : brown
CuCl2*H2O : light green
Cu(acac)2 : blue-gray

FeCl2 : blue-green
FeCl2*H2O : light green
Fe(acac)2 : red brown

Preparation of VO(acac) 2

Weight of V O used: 2 5 2.5211 g

Weight of hydrated Na CO : 10.00 g 2 3

Weight of dried VO (acac) : 4.41 g 2

V O + 4H 2(VO) + 2H O + 1/2O
2 5
+ 2+
2 2 (1)

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

2+ +
2 (2)

No. of moles of V O used = 2.5221g / (50.94 x 2 + 5 x 16.00)g/mol = 0.01387 mol

2 5

Using equation 1 and 2, each mole of V O yields 2 moles of (VO) and hence 2 moles of VO (acac) .
2 5
2+
2

No. of mole of VO (acac) = 0.01387 mol × 2 = 0.02773 mol

2

Mr of VO(acac) = (50.94 + 16.00) + 2×(5 × 12.01 + 7 × 1.008 + 2 × 16.00) = 265.15 g mol

2
-1

Theoretical yield of VO(acac) = (265.15 g/mol) × 0.02773 mol =7.352 g

2

Percentage yield of VO (acac) = 4.41 / 7.352 x 100% ≈ 60.00 % 2

Absorbance of VO (acac)2 at 506nm in chloroform

A= ecl

ϵ= A/cl
ϵ=0.267 / ((0.0668/265.159)/0.025) *1cm

ϵ= 0.267/0.0101M*1cm= 26.435 M-1cm-1

Preparation of Cu(acac) 2

Weight of CuCl2 used: 4.089g

Weight of dried Cu(acac) : 8.0635g

2

CuCl2*2H2O + H(acac) + NaCH3COO (1)

Cu(acac)2 + H2O + CH3COOH + NaCl (2)

𝑚𝑎𝑠𝑠
No. of moles of CuCl2 used =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

=4.089𝑔 / (63.546 + 2 x 35.453 )g/mol

= 0.03041 mol

Using equation 1 and 2, each mole of CuCl2*2H2O yields 1 mole of Cu(acac)2 hence

No. of mole of Cu(acac) =0.03041 mol

2

Mr of Cu(acac) =(63.546 + 10 x 12.0107 + 16 x 1.00794 4 x 15.9994)g/mol = 265.159g /mol

2

Theoretical yield of Cu(acac) = (265.159 g/mol) × 0.03041mol =8.0635g

2

Percentage yield of Cu(acac) = 4.089/8.0635 x 100% ≈ 92.00 %

2

According to Beer-Lambert’s law, A= ϵcl, at 480nm in chloroform

ϵ= A/cl

ϵ=0.55 / ((0.0661/265.159)/0.025) *1cm

ϵ= 0.55/9.9714*10-4 M*cm

ϵ=551.5775 M-1cm-1

Preparation of Cu(acac)2

Weight of FeCl2 used: 3.3682𝑔

Weight of dried Fe(acac) : 9.3873𝑔

3
FeCl2*H2O + 3(acac)H(aq) + NaCH3COO (1)

Fe(acac)3(aq) + 6H2O(l) +3H(aq) +NaCl (2)

𝑚𝑎𝑠𝑠
No. of moles of FeCl2 used =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

=3.3682𝑔 / (55.845 +2 x 35.453)g/mol

= 0.02658 mol

Using equation 1 and 2, each mole of FeCl2*2H2O yields 3 mole of Fe(acac)3 hence

No. of mole of Fe(acac) = 0.02658 x 3 mol

3

= 0.07974 mol

Mr of Fe(acac) =(55.845 + 15 x 12.0107 + 24 x 1.00794 6 x 15.9994)g/mol = 356.1925g/mol

3

Theoretical yield of Fe(acac) = (356.1925g/mol) × 0.07974)/3= 9.4676g

3

Percentage yield of Fe(acac) = 3.3682/9.4676 x 100% ≈ 35.57 %

3

Discussion:

From the IR spectra, it was observed that the V=O stretching mode of VO(acac) was at 997cm
2
-1

while that of VO(acac) py, 965.3cm . The addition of pyridine into the square geometric VO(acac)
2
-1
2

complex caused the vibration frequency of V=O stretching to decrease by 31.7 cm . When the -1

pyridine forms coordinate bond with the VO(acac) , it introduces a lone pair of electrons from
2

nitrogen into the d-orbital of the oxovanadium ion. This increases the electron density around the
vanadium ion and thus, results in electron-electron repulsion between the V=O bond. To minimise
the repulsion, V=O bond lengthens and weakens. Therefore, the band shifts to a lower
wavenumber.

Significant peaks in Significant peaks in Significant Comments

VO(acac) (cm )
2
-1 Cu(acac) py (cm )
2
-1 Peaks in
Fe(acac)3

There are not many significant differences between the 2 spectra of the VO(acac) complex and the
2

pyridine adduct except the disappearance of some peaks at 1569 cm and 997 cm . This may be
-1 -1

attributed to the presence of pyridine which affects the absorption peaks due to the distortion of
the adjacent bonds. The disappearance of the 997cm peak shows that there is complete reaction
-1

of VO(acac) . In general, the two spectra are fairly similar for the 2 complexes have similar
2

structures.
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
(pyridine, toluene and acetylacetone) were also placed away from naked flames.

Experimental techniques

To encourage even boiling, pieces of boiling chips were added to the round bottom flask during
reflux.

Also, the solution of (VO) was not filtered with cotton wool, which was suggested by the lab
2+

manual. Instead, filter papers were used. This was because cotton cool may be easily dislodged and
thus, allow unreacted V O to pass through. By contrast, filter paper is more effective at separating
2 5

the insoluble unreacted reagent and soluble product .

[4]

A magnetic stirrer should be added to the round bottom flask to further ensure homogenous mixing
of the reagents, thereby speeding up the reaction.

Conclusion

The preparation and chemical analysis of oxovanadium acetylacetonate and its pyridine adduct
allow their chemical properties to be characterised. The percentage yield of VO(acac) was 60.00%
2

while that of VO(acac) py, 63.2%. The V=O stretching shifted from 997 cm in VO (acac) to 965.3 cm
2
-1
2
-

1in VO(acac) py.

2

References

[1] Bis(4,7-dimethyl-1,10-phenanthroline) Sulfatooxovanadium(IV) as a Novel Apoptosis-inducing

Anticancer Agent. D’Cruz J. Osmond, Dong Yanhong, Rama Krishna Narla and Uckun Fatih M.
American Association for Cancer Research, 2007, article retrieved on 12/02/12:
http://orgchem.colorado.edu/hndbksupport/specttutor/irchart.html

[2] Antitumor activities of vanadium(IV), manganese(IV), iron(III), cobalt(II) and copper(II)

complexes of 2-methylaminopyridine. El-Naggar M. M., El-Waseef A. M., El-Halafawy K. M., El-Sayed
I. H. Cancer Lett., 133: 71-76, 1998.

[3] Coordination Chemistry: Reactions of Complexes. Shriver and Atkins. Inorganic Chemistry, 5 th

Edition, Oxford University Press, 2009.

[4] The Interactive Chemistry Laboratory Manual (ICLM), reference retrieved on 14 Jan 2012:
http://courseware.nus.edu.sg/iclm/default.asp