Experiment 6: PREPARATION OF BIS(ACETONATO)COPPER(II)

Objective
To synthesise Bis (acetylacetanato) copper (II) compound by using Copper
(II) Nitrate as starting material

Introduction

Complexes consist of a central metal ion or atom surrounded with a number of

other molecules or ions. It is attaches 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 bond 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 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. (Cann, 2015)
Apparatus
Filter paper, Buchner funnel, adapter, suction filtration flask, spatula,
graduated cylinder, watch glass, glass rod, pipette
Materials
Distilled water, copper (II) nitrate (Cu(No3)2.3H2O), 1:1ammonia solution,
acetyl acetone

Procedure
1. Weigh about 6g of copper(II) nitrate (Cu(No3)2.3H2O) and record down
the reading, than dissolve in 60cm3 of water.
2. Than add the 1:1 ammonia solution slowly with stirring until the
precipitate first formed has just redissolved.
3. Continuing to stir the solution than add 6cm3 drop wise of acetyl acetone
solution.
4. Filter off the crude product by using a suction filtration. Than wash it
well with water and drain it though.
5. Weigh the yield and record down the reading.

Results
Mass of copper(II) nitrate (Cu(NO3)2.3H2O) : 6.0570g
Mass of residue : 10.5782g

Discussion
Cu(NO3)2 + 4NH3 (Cu(NH3)4(NO3)2

Cu(NH3)42+ + 2NO3- + C2H8O2 + C10H16CuO4 + 4NH3 + N2 + 3O2

From the equations above we can conclude that: 1 mol of Cu2+ produces 1
mol of Cu(NH3)42+

and

1 mol of Cu(NH3)42+ produce 1 mol of C10H16CuO4

Number of mol of copper(II) nitrate = mass = 6.0570g = 0.0323mol
187.554 187.554

0.0323mol of Cu(NO3)2 : 0.0323mol of C10H16CuO4

Theoretical mass of C10H16CuO4 = 0.0323mol x 263.764 g/mol = 8.520g

Percentage of yield = 10.5782g x 100% = 124.16%

8.520g

The main purpose of this experiment is to produce

bis(acetylacetonato)copper(II), which is a coordination compound by using
precipitation and recrystallization method. Coordination compounds are
compounds that contain coordination complex. Coordination complex is the
product of a Lewis acid-base reaction in which neutral molecules or anions
(called ligands) bond to a central metal atom (or ion) by coordinate covalent
bonds. Bis(acetylacetonato)copper(II), has a molecular weight of 263.76, a
melting point of 279-2830C, it's also odorless and is neutral. Firstly, 6g of
Copper (II) nitrate, (Cu(No3)2.3H2O), dark blue crystals, is dissolved in water
and a clear blue solution is obtained. This blue solution formed indicates that
copper(II)nitrate is soluble in water and produce hexaaquacopper(II) ions and
nitrate ions. Cu(NO3)2 + 6H2O --> Cu(H2O)62+ + 2NO3 - After that, small
amount of concentrated ammonia is added to the solution with stirring until
the precipitate formed has just dissolves. Stirring is done to increase the level
of solubility. After concentrated ammonia is added, ammonia will attach itself
to the central copper ion using the lone pair electrons on the nitrogen atom
which is acting as a Lewis base because it is a lone pair donor to form a metal
hydroxide. Therefore, a pale blue precipitate of copper (II) hydroxide is
formed. When more concentrated ammonia is added, the ammonia will
replace the molecules bonded to the central atom to give another soluble
complex. This process is a ligand exchange reaction and it involves
equilibrium such as the one shown below: However, this is a slightly
untypical case, because only four of the six water molecules get replaced to
produce the tetraamminediaquacopper(II)
Bis (acetylacetanato) copper (II) compound with a chemical formula of
C10H16CuO4 with a molecular mass of 263.764g/mol. Have a hydrogen bond
donor count of 2, hydrogen bond accepter count of 4 and complexity of 239.
Topological Polar Surface Area 74.6 A^2.

Melting point of Bis (acetylacetanato) copper (II) will be 284 C degree

(decomposes). Slightly soluble in water; soluble in chloroform. (Lide, 1998-
1999)

Bis(acetylacetonato)copper(II) was sensitized by some ketones undergo

photodecomposition with a wide range of triplet energies to give the same
products as that obtained in the direct photolysis but with much better
efficiency. Not all of the reactants can success to form the reaction, for
example such as fluorenone and aromatic hydrocarbons failed to form the
reaction. There exists no correlation of the sensitizer triplet energies with the
sensitization results. This, and rapid quenching processes, indicated that the
classical energy transfer process was unlikely. The sensitization process by an
electron transfer within an encounter complex was proposed to explain the
decomposition of Cu(NO3)2, the calculated free energy changes (ΔG)
associated with the electron transfer from the available data support the
proposal. (Gonzalo Buono-Core, 1979)
Conclusion
The percentage of yield of preparation of bis(acetylacetonato)copper(II) out of
6.0570g of copper (II) nitrate in this experiment was 124.16%, where
theoretical yield is 8.520g and the experiment yield is 10.5782g
While doing the suction filtration for the crude product, after empty the
solution from the beaker than wash it with water and drain though it but we do
not wait till the crude production to be filter until it dry we have already turn
off the power supply. Therefore, the product may have contain with some
water and causing the final mass to be more than it should be. Precaution
steps: 1. Advisable not to inhale very close when weighing the products
because material is irritating to mucous membranes and upper respiratory
tract. 2. Wear gloves and be patient and careful when conducting with
concentrated chemical; to reduce the risk of injury. 3. Switch off the fans
when weighing the material as to prevent any error in reading that may
include the mass of the foreign matters. 4. Tong is used when taking the
product out from an oven because the watch glass is hot and injure the hands.
5. Do not inhale tremendously when handling acetylacetone because is sting
to the nose.

Ammonia molecule is the ligand, in that they form dative bonds to Cu2+ with
their lone pairs of electrons. A complex ion is an ion Cu2+ surrounded by
ligand. Bis(acetylacetonato)copper(II) have coordination number of 2 and
square planar shape.
References
Cann, P. a. H. P., 2015. Cambridge International AS and A Level Chemistry. s.l.:Hodder Education.
Gonzalo Buono-Core, K. I. Y. L. C. T. K. A. K. J.-I. H., 1979. Sensitized photolysis of
bis(acetylacetonato)copper(II); general reaction pattern. Canadian Journal of Chemistry, pp. 8-16.
Lide, D. (., 1998-1999. CRC Handbook of Chemistry and Physics. 79th ed. s.l.:s.n.