Title: Preparation of Bis(acetylacetonato) Copper (II)

Objective: To synthesise the bis(acetyltonato) copper (II) complex

Introduction:

A ion with metal ion as its centre and with a number of other molecules or ions
surrounding it is called a complex ion. These can be considered to be attached to the central
ion by coordinate (dative covalent) bonds. Coordinate bond is actually a covalent bond in
which both electrons come from the same atom. Ligands are the name given to the ionsor
molecules surrounding the central metal ion. Water, ammonia, acetyl acetone and chloride
ions are examples of simple ligands.

There are active lone pairs of electrons in the outer energy level of the ligands. These
pairs of electrons are used to form coordinate bonds with the metal ion. All ligands are lone
pair donors. It can also be said that, all ligands work as a Lewis base. Based on the Lewis
acid-base theory, an acid is said to be an electron pair acceptor whereas a base is said to be a
electron pair donor. Ligands are able to donate a pair of non-bonding electrons into a non-
occupied orbital of a central metal ion and thus, coordinate bonds hold a complex together.

In a nutshell, the non-occupied orbital of the central metal ion can act as a Lewis acid.
Hence, the metal-ligand is formed when the ligands act as the Lewis base by donating a pair
of electrons.

Materials: Copper (II) nitrate, water, ammonia, acetyl acetone

Apparatus: 100mL beaker, glass rod, dropper and vacuum suction

Procedure:

1. 6g of copper (II) nitrate Cu(NO3)2 was dissolved in 60cm3 of water.

2. The solution of 1:1 ammonia was slowly added with stirring, until the precipitate first
formed has just redissolved

3. Continuing to stir the solution, 6cm3 of acetyl acetone was added dropwise.

4. The crude product was filtered out by using suction filtration

 5. Then, it was washed well with water and drained thoroughly.

6. The percentage (%) yield was calculated.

Results and Calculations:

Components Amount Molecular No. of mols Theoretical yield Percentage (%)
used/ weight yield
obtained
Copper (II) 6.1203g 241.599 0.02533 6.6815g 75.57%
nitrate
Ammonia 20mL 17.031
Acetyl acetone 6.10mL 100.13 0.0609
Bis 263.78
(acetylacetonato)

Mass of copper (II) nitrate: 6.1203g

Mass of empty beaker: 3.5141g

Mass of beaker + crude product after drying in oven: 8.5634g

Mass of crude product = 8.5634 – 3.5141

= 5.0493g

Given molar mass of copper (II) nitrate is 241.599 g/mol

No. of moles of copper (II) nitrate = 6.1203/241.599

= 0.02533 mol

Assume that No. of moles of crude product = No. of moles of copper (II) nitrate = 0.02533
mol

Given molar mass of crude product: 263.78 g/mol

Theoretical yield of crude product = No. of moles of crude product x molar mass

= 0.02533 x 263.78
 = 6.6815g

Percentage (%) yield = (Actual yield / Theoretical yield) x 100%

= (5.0493 / 6.6815) x 100%

= 75.57%

Discussion:

Copper is a transition element which forms complex ions by being the central metal
atom. This central metal atom accepts the donated pair of electrons from the ligands which are
usually no-metallic ions or molecules to form dative bonds (Tan 2013). Certain reactions can
still be undergone by copper (II) nitrate to form a new coordination compound because copper
(II) nitrate is originally a coordination compound. In this experiment, copper (II) nitrate was
used to synthesise the copper (II) acetylacetonato by exchanging the ligands through several
steps.

An approximate value of 6g of solid copper (II) nitrate was weighed using the weighing
balance. Then, the copper (II) nitrate was added to 60cm3of distilled water where a pale blue
solution of copper (II) hexaaqua complex was formed

Cu(NO3)2 (aq) + 3H2O (l) [Cu(H2O)6]2+(aq) + 2NO3-(aq)

Copper (II) nitrate hexaaqua copper (II) complex

Then, the hexaaqua copper (II) complex (pale blue solution) was added with 1:1
ammonia to form copper (II) hydroxide solution. In this reaction, the high concentration of
water molecules which were bonded to the copper (II) was not able to be displaced by the
insufficient amount of ammonia. Instead, the hydrogen ions were pulled off of the
hexaaquacopper (II) complex by using the help of ammonia which acted as a base (Clark
2003) to form copper (II) hydroxide which was also a pale blue solution.

[Cu(H2O)6]2+(aq) + NH3 (aq) [Cu(H2O)5(OH)]+ (aq) + NH4+ (aq)

 As shown in the equation above, the equilibrium was shifted to the right to produce
more complex ions (base on Le Chatelier’s principle). The hexaaqua ions reacted with
ammonia easily than the hydrogen ions because hexaaqua ions were more abundantly presen
(Jim Clark, 2003)

[Cu(H2O)5(OH)]+(aq) + NH3 (aq) [Cu(H2O)4(OH)2] (s) + NH4+ (aq)

Precipitate of ([Cu(H2O)4(OH)2]) was formed as more ammonia was added. As

ammonia reacted with the complex ([Cu(H2O)5(OH)]+) or with hydrogen ions, the
equilibrium again shifted to the right.

When excess ammonia was added, the precipitate formed was dissolved. Since the
hexaaqua copper (II) complex dissociated to give away hydrogen ions which might have
formed ammonium ions with ammonia, the hexaaqua copper (II) complex is actually acidic.

[Cu(H2O)6]2+ (aq) + NH3 (aq) Cu(OH)2 (aq) + NH3 (aq) + 4H2O (l) + 2H+ (aq)

hexaaqua copper (II) complex copper (II) hydroxide

Or

[Cu(H2O)6]2+(aq) + NH3 (aq) Cu(OH)2 (aq) + NH4+(aq) + 4H2O (l)

hexaaqua copper (II) complex copper (II) hydroxide

There were enough amount of ammonia to displace hydroxide ions as more

ammonia was added into the solution to form tetraaminediaqua copper (II) complex. The
solution then turned dark blue.

[Cu(H2O)2]2+ (aq) + 4NH3 (aq) Cu[(NH3)4(H2O)2]2+ (aq) + 4H2O(l)

hexaaqua copper (II) complex tetraaminediaqua copper (II) complex

When acetyl acetone was added into the solution, copper (II) acetylacetonato
was formed.
Cu[(NH3)4(H2O)2]2+ (aq) + 2C5H8O2 (aq) Cu(C5H7O2)2 (aq) + 4NH3 (aq) + 2H2O(l) +
2H+(aq) acetylacetonato copper (II) complex

The solution was first filtered using suction filtration to get the product so that it can be
weighed and the dry mass of the product can be obtained. The Buchner funnel and flask were
used for the filtration process. The product was collected into a beaker as the liquid was
filtered out. The product was sent into the oven to dry. The actual mass of the product after
drying was obtained as 5.0493g.

The theoretical mass of the product was calculated by assuming that 1 mole of copper
(II) nitrate reacted to produce 1 mole of the product. Using this method, the theoretical mass
was calculated as 6.6815g and a percentage yield was 75.57%.

For precaution purposes, direct contact was avoided when handling hexaaqua copper
(II) and copper (II) hydroxide solutions as they are acidic. As another precaution measure, the
filter paper on the Buchner funnel was drenched with distilled water to prevent the filtration
to occur through the funnel to the Buchner flask. Furthermore, the product was washed with
distilled water to remove impurities and also dried well to get maximum yield.

Conclusion:
The percentage yield of acetylacetonato copper (II) complex is 75.57%

Question and Answer

1. Draw the structure of the complex

2. Describe the structure by mentioning the ligating atoms of the ligand and its
geometry. Discuss the synthesis of the complex.

Acetylacetonate is the ligand. Acetylacetonate, is a common bidentate ligand which is a

colourless solution. Complexes with many transition metal ions are formed by
acetylacetonate anion. Bidentate ligands have two lone pairs, both which are able to bond
with the central metal ion.

CH3 – C(O) – CH2 - CH2 – C(O) – CH3

Through the lone pair of oxygen, acetylacetonate is bonded. Acetylacetoanato copper (II)
complex has a square planar monomeric copper (II) complex shape which makes it
unique among the metal complexes of acetylacetonato. The acetylacetonato anion is able
to form complexes with many transition metal ions. The reaction of acetylacetone with
metal ion in the presence of a base is a general method of synthesis where the base helps
with the removal of a proton from acetylacetone and the equilibrium is shifted in favour
of the complex. A six-membered chelate ring is formed when both the oxygen atoms
bind. No added base in needed in some cases where
References
1. Clark, 2003. Chemguide. [Online]
Available at: http://www.chemguide.co.uk/inorganic/transition/copper.html
[Accessed 27 January 2018].
2. Tan, 2013. Ace AHead STPM Text Chemistry Second Term. In: Selangor Darul
Ehsan: Oxford Fajar.
3. Yip, 2013. Pre-U STPM Text Chemistry Term 2. In: Selangor Darul Ehsan: Pelangi.