Title: Synthesis of Metal Acetylacetonates

Objective: To prepare tris(acetylacetonato)manganese(III), Mn(acac)3 {also called tris(2,4pentanedionato)manganeses(III)}

Introduction:
Coordination complexes consist of a central metal atom surrounded by various other
atoms, or small molecules called ligands. It is important to recognize the nature of the ligand the availability of coordination sites or ligating atoms and the conditions under which these are
available for coordination. To obtain the oxidation state of the metal in the complex to be
synthesized may require prior oxidation or reduction of the starting material (metal salt). In the
presence of a base, acetylacetone (= 2,4-pentadione) readily loses a proton to form the
acetylacetonate anion, acac-. Hydrogen atoms on -carbon atoms that are adjacent to
carbonyl (C=O) groups are relatively acidic. The diagram below shows the structure of
acetylacetonate ion.

In this experiment, we will prepare and characterize complexes of 2 metal ions with the
anion of acetylacetone. Acetylacetone (2,4-pentanedione) is a typical -diketone that can
ionize in aqueous solution as a weak acid:

CH3C(=O)CH2C(=O)CH3

H+ + [CH3C(=O)CHC(=O)CH3]-

The acetylacetonate has three different representations called resonance forms. This
ligand is a bidentate and coordinate through its two oxygen atoms. Transition metals have
variable oxidation state. In their complexes, the number of outer valence electrons vary with the
oxidation state. Since electrons spin and generate a magnetic field, the magnetic properties of
transition metals (in their complexes) are of great interest in determining the oxidation state,
electronic configuration, and so on. The magnetic moment of the metal is determined indirectly
from the magnetic susceptibility.
When a ligand is bounded to a central metal through a single donor atom, then the ligand
is known as unidentate (the ligand binds to the metal through a single point of attachment as it
has one tooth). For a bidentate ligand, it can use two atoms donor to bind to a metal. Larger
ligands may contain more than one capable of coordinating bonds which bonded to a single
central metal. These kind of ligands are known as polydentate. When a bi- or polydentate ligand
uses two or more donor atoms to bind to a single metal ion, it is said to form a chelate complex.
Such complexes tend to be more stable than similar complexes containing unidentate ligands due
to chelating effect.

The resulting acetylacetonate anion can serve as a ligand to metal ions, forming
complexes in which the ligand is bonded to the metal through both oxygen atoms to form a sixmembered ring. The six-membered rings (MO2C3) are planar and weakly aromatic because they
contain 6 electrons. In complexes of stoichiometry M(acac)3, the MO6 array is octahedral and
in VO(acac)2, the VO5 group is square pyramidal. In general the complexes are neutral and may
be isolated as crystalline solids having an interesting variety of colors. The common structure for
the synthesis of metal acetylacetonate was shown.
CH3

H3C

Target Molecules

O
M

O
O

O
H3C

CH3

In pure acetylacetone, or solutions of acetylacetone in non-polar organic solvents, the

diketo formed is in equilibrium with a cyclic enol-like form. This second tautomer may be
regarded as a complex in which the proton takes the role of the metal ion Mn+.

Apparatus:
Conical flask, Measuring cylinder, Glass rod, Hot-plate stirrer, magnetic bar, Thermometer,
Beaker, Sintered funnel, FTIR spectrometer
Materials:
Manganese(II) chloride tetrahydrate, Sodium acetate trihydrate, Acetylacetone, Potassium
permanganate solution, Acetone
Procedure:
1. 5g (0.025 mol) manganese(II) chloride tetrahydrate (M.W. 197.90) and 1.3 g(0.0095 mol)
sodium acetate trihydrate (M.W., 136.08) were dissolved in distilled water (200 cm3) and to the
stirred solution add slowly 21 cm3 (~0.20 mol) acetylacetone .
2. The resultant two-phase system was treated with potassium permanganate solution (1 g in 50
cm3 of water).
3. After a few minutes, small amounts with stirring, another sodium acetate solution (13 g or
0.095 mol of the sodium acetate trihydrate in 50 cm3 of distilled water) was added.
4. The solution was heated to about 60 C with continuous stirring for about 30 minutes.
5. The resultant solution was cooled in ice-cold water and then the solid complex formed was
filtered by suction filtration. The complex was washed with acetone and suck dry.
Results and calculations:

Weight of manganese(II) chloride tetrahydrate, MnCl2.4H2O = 5.0256 g

Weight of first protion of sodium acetate trihydrate, Na(acac)3 = 1.3065 g
Weight of potassium permanganate, KMnO4 = 1.0200 g
Weight of second portion of sodium acetate tirhydrate, Na(acac)3 in 50cm3 distilled water =
13.0050 g
Weight of empty beaker: 50.5668 g
Weight of beaker + product, Mn(acac)3 : 56.1500 g
Weight of product, Mn(acac)3 : 5.5832 g
Purity of acetylacetone = 100%
Density of acetylacetone = 0.975g/cm3
Mass of acetylacetone = density x volume used
= 0.975g/cm3 x 21cm3
= 20.475g
Molecular mass of acetylacetone = [(12.01x5) + (16x2) + (1.008x8)] g/mol
= 100.11 g/mol
Number of mole of acetylacetone used = Mass/ Molecular mass
= 20.475g / 100.11g mol-1
= 0.2045 mol
Molecular mass of manganese(II) chloride tetrahydrate
= [54.94 + 35.45(2) + 4 (18.016)] g/mol = 197.90 g/mol
Number of mole of manganese(II)chloride tetrahydrate = 5.0256 g / 197.90 g mol-1
= 0.0254 mol
Molecular mass of Mn(acac)3
= [54.94 + 3(12.01x5 + 16x2 + 1.008x7)] g/mol= 352.258 g/mol
Number of mole of Mn(acac)3 = 5.5832 g/ 352.258g mol-1
= 0.0158 mol

No of mole of KMnO4 = 1.0200 g / 158.0339 g mol-1

= 0.0065 mol
4 Mn2+ + MnO4- + 15 Hacac 4 H2O + 7 H+ + 5 Mn(acac)3
From the equation, 1 mole of MnO4- produced 5 mole of Mn(acac)3.
Theoretical mass of Mn(acac)3 = 5 x 0.0065 mol x 352.2617 g/mol
= 11.4485g
Percentage yield of Mn(acac)3 = 5.5832 g /11.4485 g x 100%
= 48.77 %

49 %

The magnetic moment of Mn(acac)3:

Charge of Mn3+ = +3
Total number of electron in Mn atom = 25
Number of electron in Mn3+ ion = 22
Eletron configuration of Mn3+ : [Ar] 3d4
s = g s(s+1)
= 2 2(2+1)
= 4.90B

Discussion:
The coordination number of a metal complex is determined directly from the number of
ligand that can be accepted by a transition metal. In order to obtain the oxidation state of the
metal in the complex to be synthesized, this may need prior oxidation or reduction of the starting
material. The metal salt, manganese(II) chloride tetrahydrate is the starting material in this
experiment. In the presence of a base, the acetylacetone is readily to lose a proton to form the
acetylacetone anion, acac- through monodeprotonation of acetylacetone. Hydrogen atoms on the
carbon atoms that are adjacent to carbonyl (C=O) groups are relatively acidic. In the isomerism,
the acetylacetonate ion has three resonance forms. This ligand is a bidentate which used its two
oxygen atoms to coordinate by donating lone pair electrons towards central metal.
In this experiment, the manganese complex is a good example of octahedral complex
which containing three bidentate ligands. The structure of the Mn(acac)3 complex was shown.

The metal ion is electrically neutral because it is carrying a 3+ charge and each ligand carried -1
charge. The complex is more soluble in organic solvent than water due to its neutral properties.
Manganese exhibits an unusually wide range of oxidation state which includes +7 to -1, but in
aqueous solution the +2 oxidation state is the most common. The three bidentate ligands are
pack very efficiently around the trivalent ions of transition metal. As a result, the Mn2+ can be

easily to be oxidized to form Mn(acac)3 in the presence of acetylacetonate ions. Oxidizing agent
(potassium permanganate solution) is used to oxidize the four equivalent of Mn2+ to become
Mn3+ as shown in the equation below:
MnO4- + 4Mn2+ + 8H+ 5Mn3+ +4H2O
The formation of Mn3+ ions are used to react with acetylacetonate ions to produce
Mn(acac)3. At the same time, the deprotonation of acetylacetone will produce a large amount of
H+. In order to maintain the acidity of the solution, the sodium acetate is added to neutralize the
acid released which proton reacts with acetate ion to form weak acetic acid.
7H+ + 7CH3COO- 7CH3COOH
The overall equation can be written as:
4M n
7H

2+

+M n O

+ 1 5 C H 3C O C H 2C O C H

+ 7 C 2H 3O

7 H C 2H 3O

5 M n (C H 3C O C H C O C H 3)3 +4 H 2O

+ 7H

When treating the resultant two-phase system with potassium permanganate solution, if
the solution was not stirred well, there will be solids left behind. Hence, it had to be put more
distilled water to dissolve it completely. After few minutes, a small amount of another sodium
acetate solution was added with stirring. Although it was about 13 g to be added in but it was
considered as small amounts due to it was a weak acid. A lot of base was added in which caused
the neutralization reaction occurred when this solution was added to it.
Acetylacetone (2,4-pentanedione) is a -diketone. The reaction is dehydrogenation. 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 (as
shown below):

To reduce the H+ ions in the structure, the reaction will continuously goes to right hand side and
it is irreversible. Therefore, a higher and better yield of product can be obtained.
The potassium permanganate solution was not transparent in colour. In fact, it was in
purplr colour which was difficult to see through when dissolved the mixture of manganese(II)
chloride tetrahydrate and 1.3 g(0.0095 mol) sodium acetate trihydrate. It was made sure the
solution was stirred for quite a while. This is because the KMnO4 solution was difficult to
dissolve and its colour made it hard to see if it had dissolved.
Cooling the metal complex product was a critical step in this synthesis procedure. It
allowed to grow larger crystals in low temperature that are more suitable for IR structural
analysis. The IR spectrum of the product, Mn(acac)3 was observed. The functional groups that

characterize the product are CH3, -C-H, alkenes and carbonyl compounds. According to the
spectra, the C=O peak can be observed at 1582 cm-1 while comparing to the theoretical value
(1680 1630 cm-1), which confirms the presence of carbonyl group in the structure of
Mn(acac)3. Next, the CH3 bend observed at 1376 cm-1 shows the presence of CH3 in the
product. This matched the band position of alkene. Another C-H alkene (out-of-plane bend)
was indicated at 1016 670 cm-1 range. It was quite near to its basic range of about 1000 - 650
cm-1. C=C bond can also be seen at the range of 1513 cm-1. The basic value of alkene band is
1680-1600 cm-1. In the experimental spectrum compared to the sample spectrum, there was a
OH group stretch at the range of 3436 cm-1. This means that the complex was still containing
some water in it and thus means it was not completely dry.
The percentage yield was only 49% may be due to several factors that caused the loss of
products. One of the factors is that the solution was not saturated enough to produce maximum
yield of Mn(acac)3 after cooling. Normally, larger volume of solvent used will tend to make the
products to dissolve more easily. When transferring the product to weigh its weight, some of the
product may spill out. The product may left on the filter paper during the transfer of product to
weigh. The additional acetone need to be added which also caused the solution to be dissolved.
Therefore, the product was lost in the solution.
In the drying condition of the product, acetone was used to wash the product. This is
because if the solvent is distilled water, it may alter the analysis of IR spectrum of Mn(acac)3.
The OH group in the water may give a signal in the analysis thus may caused some variations
in the analysis. Besides, if the acac- ion keep contact with water, it may be further oxidized and
thus made the product yield decreased.
There were a few precautions to be done in this experiment. As the reagents may be
toxic, gloves were worn to protect the hands. This is especially important when handling
corrosive reagents such as potassium permanganate solution. The flammable reagents such as
acetylacetone was placed away from naked flames.
Conclusion:
The metal acetylacetonate, Mn(acac)3 was formed in this experiment. The percentage yield of
Mn(acac)3 was only 49%. The functional groups that characterize the product are CH3, -C-H,
alkenes and carbonyl compounds.
References:
Mn(acetylacetonate)3 , nd. Available from:
<http://www.chemistry.wustl.edu/files/chemistry/imce/Mn-acetylacetonate-3.pdf> [Accessed on
4 March 2014]
Ha, ST 2014, Chapter 2-Infrared Spetroscopy, lecture notes distributed in UDEC 2124 Applied
Spectroscopy at Universiti Tunku Abdul Rahman, Kampar on 22 January 2014.