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Name: Kavisha a/p Sundraraj

ID: 1205675

Partner: Chong Yan Jie

Practical group: P (3)

Experiment details: -

Number: 2

Title: BIOINORGANIC CHEMISTRY:PREPARATION OF


BIS(ACETYLACETONATO)OXOVANADIUM(IV), [VO(acac)2] AND ITS
PYRIDINE ADDUCT [VO(acac)2Py]

Date: 2 FEBRUARY 2017

Submission date: 7 APRIL 2017

Lecturer: DR.OOI MEI LEE


Title: Bioinorganic Chemistry: Preparation of Bis(acetylacetonato)oxovanadium(IV),
[VO(acac)2] and its Pyridine adduct, [VO(acac)2Py]

Objective: (i) To prepare [VO(acac)2] and its pyridine adduct of [VO(acac)2Py].

(ii) Characterisation of the oxovanadium(IV) complexes with IR spectroscopy

Introduction:

Vanadium is a transition element with partially filled d-shell. The formation of


compounds of vanadium complexes whose colour is due to d-d electronic transitions; such as;
[V(H2O)6]+2 (purple), [V(H2O)6]+3 (green), [VO(H2O)5]+2 (blue) and [VO(H2O)5]+3 (yellow).
The formation of compounds in many oxidation states due to the relatively low reactivity of
the d unpaired electrons; example: V2+, V3+, V4+, and V5+. The formation of paramagnetic
complexes is due to the presence of unpaired d electrons. However, the most stable oxidation
state for vanadium is +4.

Vanadium(V) oxide is with the formula V2O5. Commonly known as vanadium


pentoxide, it is a brownish yellow solid, but when freshly precipitated from aqueous solution,
its colour is deep orange. Due to its high oxidation state, it is both an amphoteric oxide and an
oxidizing agent.

Acetylacetone (2,4-pentanedione) is a -diketone. 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 stablised 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:

Refluxing with pyridine causes further metal-ligand coordination and produces VO(acac)2Py.
IR spectroscopy is useful then in distinguishing between the vibrational energies of the dark
blue-green VO(acac)2 and greyish VO(acac)2Py.
Apparatus:

250 ml conical flask

250 ml beaker

10 ml measuring cylinder

Glass rod

Heating mantle

Round-bottom flask with vertical condenser

Buchner funnel

FTIR spectrometer

Materials:

Vanadium(V) oxide

Absolute ethanol

Acetylacetone

Anhydrous sodium carbonate

Dichloromethane

Diethyl ether

Concentrated sulphuric acid

Toluene

Pyridine

Procedure:

Part I: Preparation of Bis(acetylacetonato)oxovanadium(IV), VO(acac)2

1. 1.0 g of vanadium(V) oxide was weighed into 250 ml round-bottom flask.

2. 5 ml of distilled water was added together with 3 ml of concentrated sulphuric acid


and 10cm3 absolute ethanol.

3. The mixture was refluxed by using heating mantle. The mixture was swirled while
heating to avoid any precipitate formed at the wall of the round bottom flask.

4. After an hour, the colour of mixture turned from green and blue.
5. A little ethanol was added to make the dark solution less viscous. The solution was
filtered through a cotton wool.

6. The filtrate was transferred to 250 ml beaker and was added with 3.5 ml
acetylacetone.

7. The solution was neutralised by adding slowly and stirring a solution of 10 g


anhydrous sodium carbonate in 60 ml of distilled.

8. The product was filtered and dried in air.

9. The product was recrystallized. The product was dissolved in minimum warm
chloroform.

10. The impurities were filtered and the filtrate was cooled in an ice bath.

11. About 10-20 ml diethyl ether was added until precipitate occurs.

12. The product was filtered, washed with cold ether and air dried. The yield was
recorded.

Part II: Preparation of Pyridine Adduct, [VO(acac)2Py]

1. The half of the product from Part 1 was dissolved in about 20 ml toluene and was
refluxed for 30 minutes with a large excess (6 ml) of pyridine.

2. The resultant solution was concentrated to a smaller volume by distilling off the
toluene and pyridine.

3. The solution was cooled down and crystals were formed in ice bath.

4. A small amount of ether was added.

5. The final product was filter and dried in desiccator.

6. The yield of final product was recorded.

Results:

Part 1:
Mass of V2O5 1.0019 g
Mass of petri dish 33.2020 g
Mass of VO(acac)2 with petri dish 34.7790 g
Mass of VO(acac)2 1.5770 g

Part 2:

Mass of VO(acac)2 1.5770 g


Mass of plastic bag 1.2273 g
Mass of VO(acac)2Py and plastic bag 1.9067 g

Mass of VO(acac)2Py 0.6794 g

Calculations:

Part 1:

V2O5 + C2H5OH + 2H2SO4 2VOSO4 + CH3CHO + 3H2O ---- (1)

VOSO4 + 2C5H8O VO(C5H7O)2 + H2SO4 ----- (2)

Equation (1) and (2) are multiply with 2;

1V2O5 + 4(C5H7O-) 2VO(acac)2

Molar mass of V2O5 = 181.88 g/mol

mass
Mole of V2O5 =
molar mass

1.0019 g
=
181.88 g/mol

= 5.509 x 10-3 mol

Since, 1 mole of V2O5 = 2 mole of VO(acac)2

Thus, the mole of VO(acac)2 = 5.509 x 10-3 mol * 2

= 0.011 mol

Molar mass of VO(acac)2 = 265.157 g/mol

Theoretical mass = molar mass * mole


= 265.157 g/mol * 0.011 mol

= 2.92 g

actual mass
Percentage yield = * 100%
theoretical mass

1.5770 g
= * 100%
2.92 g

= 54.0 %

Part 2:

1VO(acac)2 + Py 1VO(acac)2Py

1.5770 g
Mole of VO(acac)2 = mole of VO(acac)2Py =
265.157 g /mol

= 5.947 x 10-3 mol

Theoretical mass = 344.26 g/mol * 5.947x 10-3 mol

= 2.047 g

0.6794 g
Percentage yield = * 100%
2.047 g

= 33.19 %

Discussion:

In the first part of the experiment, Vanadium pentoxide, V2O5 was refluxed with
concentrated H2SO4, water and ethanol for an hour, reduces V2O5 to (VO)2+. Orange V2O5
dissolves in the colourless solvents to form a dark green (VO)2+ solution.

1
V2O5 + 4H+ 2(VO)2+ + 2H2O + O2
2

The vanadium (II) ion, VO2+ was chelated with 2 acac anions to form blue-green
[VO(acac)2]. The mass recovered from recrystallization is 1.5770g with percentage yield of
54.0 %. This dark blue-green complex has a square-based pyramidal geometry and is able to
accommodate one more ligand as shown below:
bis(acetylacetonato)oxovanadium(IV)

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

Sodium carbonate, 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.

Pyridine adduct

In the second part, pyridine and the complex was mixed with toluene as the pyridine
is miscible in organic solvent. 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, is an octahedral. The mass of the complex
recovered after recrystallization is 0.6794 g with percentage yield of 33.19%.

V2O5, VO(acac)2 and VO(acac)2Py are coloured compounds 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.

The percentage yield for VO(acac)2 was 54%. This amount of yield is above 50 % and
considered to be moderate.. Theoretically, 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 amount of base may be added to favour the formation of the desired product
as well.

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 fume hood to prevent any inhalation of harmful
organic vapours. The flammable reagents such as pyridine, toluene and acetylacetone were
also placed away from naked flames. The most significant precaution in the entire
experiment is that men are to be cautious during handling the pyridine as it can cause
infertility and chronic exposure can cause harm. Boiling chips were added during reflux to
avoid bubbling. Lastly, a magnetic stirrer should be added to the round bottom flask to further
ensure homogenous mixing of the reagents, thereby speeding up the reaction.

From the IR spectra, it was observed that the V=O stretching mode of VO(acac)2 was
at 997 cm-1 while that of VO(acac)2Py, 937 cm-1. The addition of pyridine into the square
geometric VO(acac)2 complex caused the vibration frequency of V=O stretching to decrease
by 60 cm-1. When the pyridine forms coordinate bond with the VO(acac)2, it introduces a lone
pair of electrons from 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. V=O bond lengthens and weakens in order to minimise the repulsion.
Therefore, the band shifts to a lower wavenumber. The difference between these two spectra
is that in the pyridine adduct spectrum has more addition peaks compared to VO(acac)2
complex. This may be attributed to the presence of pyridine which affects the absorption
peaks due to the distortion of the adjacent bonds. However, the 997 cm-1 peak still appeared
in the pyridine adduct spectrum which means that the pyridine adduct is not pure and the
reaction was not totally completed. In general, the two spectra are fairly similar for the two
complexes having similar structures.

Exercise:

1. FTIR spectrum of the complex.

Significant peaks in [VO(acac)2], cm-1 Species


2967 -OH
1531 -CH3
1373 C-O
1019-997 V=O
937 C-C
799 C-H

2. Structure of aquabis(acetonato)oxovanadium(IV).
Conclusion:

The 1.5770 g dark blue-green complex formed in Part 1 is


bis(acetylacetonato)oxovanadium(IV) with the percentage yield of 54.0%. The complex is a
square-pyrimidal structured with 5th coordination number. The pyridine adduct is a grey-
coloured octahedral complex with mass of 0.6794 g and its percentage yield is 33.19 %. The
stretching mode of V=O and its pyridine adduct obtained are 997 cm-1 and 937 cm-1
respectively. However, the pyridine adduct complex is found to be impure. Therefore,
bis(acetylacetonato)oxovanadium(IV) and its pyridine adduct were prepared. The
oxovanadium complexes were characterized with IR spectroscopy.

Reference:

2017. Bioorganic Chemistry: Preparation of bis(acteylacetonato)oxovanadium(IV)


and its Pyridine adduct. UDEC2114 Transition Elements and Coordination Chemistry.
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[Accessed 27 March 2017].

Vanadyl acetylacetonate - Wikipedia, the free encyclopedia. 2017. Vanadyl


acetylacetonate - Wikipedia, the free encyclopedia. [ONLINE] Available
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