Title

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

Objective

: To synthesize the bis(acetylacetonato)copper(II) complex.

Introduction

Complexes consist of a central metal ion or atom surrounded with a number of other
molecules or ions. It is attached to the central ion by dative covalent which is known as
coordinate bonding. Coordinate bonding is a type of covalent bond which the electrons come
from the same atom or in other words chemical bond between two atoms when one of the
atoms shares pair of electrons.
The molecules or ions surrounding the central metal ion are called ligands . All
ligands are Lewis base. They are lone pair donors. They are nucleophilic, they donate
electron pair . The number of ligands bound to the transition metal ion is called the
coordination number. The natures of ligand are the availability of coordination sites or
ligating atoms and the conditions under which these are available for coordination.
The central metal ion acts as Lewis acid . This is because they can accept electrons,
atoms or ions. The central metal ion is with lack of octet arrangements of electrons. In the
formation of complex ions, the central metal ion must have high charge density and empty
orbitals to accept the lone pair of electrons from the ligands. So the Lewis acid which is lack
have empty orbitals accepts the lone pair of electrons from Lewis base.
The metal complexes that contain at least one ammonia (NH3) ligand are called metal
ammine complexes. Metal acetylacetonates are coordination complexes derived from the
acetylacetonate anion(acac) and metal ions. The coordination number of a complex ion is the
number of coordinate bonds being formed by the metal ions at its central.

Apparatus and Material:

Beaker, Glass rod, Measuring cylinder, Suction filtration set, Spatula, Filter paper, 6g of
copper(II)nitrate, 60cm3 of water, solution of 1:1 ammonia, 6cm3 of acetyl acetone.
Procedure:
1. 6g of copper(II) nitrate (Cu(NO3)2.3H2O) was dissolved in 60cm3 of water.
2. Slowly the solution of 1:1 ammonia was added while stirring until the precipitate that
was first formed redissolved.
3. The stirring of the solution was continued and then 6cm3 of acetyl acetone was added
drop wise.
4. The crude product was filtered off using suction filtration.
5. Then it was washed with water and drained thoroughly.
6. The percentage yield(%) was calculated.
Results:
Mass of Cu(NO3)2.3H2O

5.8732 g

Mass of filter paper

0.5812g

Mass of filter paper +

7.2550g

product
Mass of product

6.6688g

Molar mass of Cu(NO3)2.3H2O: 241 g mol-1

Molar mass of (C5H7O2)2Cu: 261 g mol-1
Colour of precipitate: Blue colour
Calculations:
Theoretical yield;
Cu(NO3)2.3H2O + 2 C5H8O2

Mass of Cu(NO3)2.3H2O

: 5.8732g

(C5H7O2)2Cu + 2 HNO3 +3H20

Mole of Cu(NO3)2.3H2O

Mass
Molar mass

5.8732 g
241 g mol1

: 0.024370 mol
From the equation, 1 mole of Cu(NO3)2.3H2O produces 1 mole of (C5H7O2)2Cu.
Number of mole of Cu(NO3)2.3H2O = Number of mole of (C5H7O2)2Cu
= 0.024370 mol
Mass of (C5H7O2)2Cu = Number of mole of (C5H7O2)2Cu x Molar mass of (C5H7O2)2Cu
= 0.024370 mol X 261 g mol-1
= 6.36057 g

Percentage (%) yield

Actual yield
x 100
T h eoretical yield

6.6688
x 100
6.36057

= 104.85%

Discussion:
Copper atomic symbol is (Cu) and the number of each electron in its shell is 2 8 8 8
3 , is in group 11 and period 4 , its atomic number is 29 . It is solid at 298 K in its standard

state with electronic configuration 1s2 2s2 2p6 3s2 3p6 4s2 3d9 . Its is one of the transition
element in the periodic table . It forms complex ions by dative bond with lone pair of oxygen
atoms in the acetyl acetone.
In this experiment, Bis(acetylacetonato)copper (II) is formed by the reaction of
hydrated copper (II) nitrate, Cu(NO3)2.3H2O and acetyl acetone, C5H8O2.
Cu(NO3)2.3H2O + 2 C5H8O2

(C5H7O2)2Cu + 2 HNO3 +3H20

Hydrated copper nitrate can be prepared by hydration of the anhydrous material or by

treating copper metal with an aqueous solution of silver nitrate or concentrated nitric acid
Cu + 4 HNO3 Cu(NO3)2 + 2 H2O + 2 NO2
Anhydrous Cu(NO3)2 forms when copper metal is treated with N2O4:
Cu + 2 N2O4 Cu(NO3)2 + 2 NO

Copper (II) nitrate is a blue crystal with a melting point of 256 C, and boiling point
of 170 C. When it is in hydrated form, it is very soluble in ethanol, ammonia, and water;
insoluble in ethyl acetate. .For the acetyl acetonates, it is crystalline powder with slightly
soluble in water but soluble in alcohol and blue in colour.
To synthesis bis(acetylacetonato) copper (II) complex, copper (II) ion and
CH3COCHCOCH3 are needed. By adding ammonia to the copper (II) nitrate, copper (II) ion
is formed. This is because ammonia is base that enables the conversion of the arrangement of
the structure so that one of the carbonyl groups in copper (II) nitrate was converted to an

acidic OH group and then gave its proton to NH3 and leaves the water-soluble
acetylacetonate ion.
To generate CH3COCHCOCH3 ion, acetylacetone is needed. Acetyl acetone is used in
the preparation of metal acetyl acetonates for catalyst application. It ables to act both as
chelating agent and solvent, which it is also a competing complex. The ammonia molecule in
the Cu (NH3)42+ ion deprotonate the acetyl acetone as ammonia is a good leaving group. With
the presence of this competing complex, the process can be done in faster rate as it speeds up
the reaction.

Below shows the convertion CH3COCH2COCH3 to CH3COCHCOCH3 :

O

H3C

CH3

H3C

O-

CH3

Therefore, Bis(acetylacetonato)copper (II) is formed by the reaction of hydrated copper (II)

nitrate, Cu(NO3)2.3H2O and acetyl acetone, C5H8O2.
There are some precautionary steps which can be taken during this experiment.
Percentage yield of this experiment is 104.85%. This is due to some errors that occurred
during experiment. The percentage yield is more than 100% because there is still presence of
ammonia in the product because perhaps it wasnt washed thoroughly. The amount of
reactants becomes lesser and lesser when going through the transfer of reactant from
apparatus to apparatus. Make sure the filter paper is in the right size to avoid the precipitate
from flowing into the suction filter which causes less product form. Parallax error must be
avoided when measure the amount of solution being used in experiment. Eyesight must be

perpendicular to the reading on measuring cylinder. Use gloves and protective goggles when
dealing with chemical substances. Switch off the fans to prevent the product been blown off.

Conclusion:
Bis(acetylacetonato)copper (II) is formed by the reaction of hydrated copper (II) nitrate, and
acetyl acetone. Hydrated copper nitrate can be prepared by hydration of the anhydrous
material or by treating copper metal with an aqueous solution of silver nitrate or concentrated
nitric acid. To synthesis bis(acetylacetonato) copper (II) complex, copper (II) ion and
CH3COCHCOCH3 are needed. The actual mass of crude product is 6.6688g and the
percentage yield is 104.85%.

References:
AN INTRODUCTION TO COMPLEX METAL IONS .Jim Clark, 2003, available from:
<http://www.chemguide.co.uk/inorganic/complexions/whatis.html >[30 January 2015]
Copper (II) acetyl acetone. Available from:
<http://www.chemicalland21.com/specialtychem/perchem/COPPER(II)
%20ACETYLACETONATE.htm >. [30 January 2015]
U.S. Secretary of Commerce on behalf of the United States of America 2011, Copper,
bis(2,4-pentanedionato-O,O')-, (SP-4-1)- . Available from:
<http://webbook.nist.gov/cgi/cbook.cgi?ID=C13395169&Mask=20> . [30 January 2015]

Questions:
1. Draw the structure of the complex.

2. Describe the structure by mentioning the ligating atoms of the ligand and its
geometry.
The copper(II) ion binds with 2 same chelate ligand, the anionic acetylacetone
ligands, which is CH3COCHCOCH3 ion. At each side of the ligand, the 2 oxygen
atoms form a bonding with the copper ion and form a six-membered chelate ring. The
keto form (CH2COCH2COCH3) and enol form (CH3COCH=C(OH)CH3) of acetyl
acetone coexist in solution. This enol-keto tautomerism (reversible interconversion of
structural isomers) results in the tautomeric migration of a hydrogen atom from an
adjacent carbon atom to a carbonyl group of a keto compound to produce the enol
form of the compound; the reverse migration of hydrogen atom is also
interconvertible, which makes the switch of a single bond and adjacent solid bond.
Besides, there are electrons delocalize at the double bond at O-C-C-C-O bond which
make the complex more stable. Bis(acetylacetonato)copper(II) is planar transition
metal complexes means its geometry is planar.