Synthesis of the metal acetylacetonates

Cr(acac)3, Mn(acac)3, Fe(acac)3, and

Co(acac)3
By: Joshua Aun

Course Code: CHY449

Group #: 2
TA: Jeff Pau
Date submitted: Jan. 28th 2016
Abstract:

The metal acetylacetonates Cr(acac)3, Mn(acac)3, Fe(acac)3, and Co(acac)3 were

successfully synthesized in this experiment. The Cr(acac)3 produced was deep purple. The
Mn(acac)3 produced was muddy brown. The Fe(acac)3 produced was bright red. The Co(acac)3
produced was dark green. The yields produced in this experiment appear to be nice, but the exact
percent yields are yet to be determined.

Introduction:

The purpose of this experiment was to synthesize the acetylacetonate complexes of the
metals Cr(III), Mn(III), Fe(III), and Co(III). The acetylacetonate ion is formed when -diketones
tautomerize in the presence of a base. The use of a base helps to deprotonate acetylacetone.
These ions are chelating and become bidentate ligands for the transition metal ions.
The complexes formed are soluble in organic solvents and this property allows them to
act as catalysts. An application of this is the use of metal acetylacetonates as catalysts in organic
synthesis or as catalysts for epoxy and anhydride curing reactions.
Some techniques used in the synthesis of these metal acetylacetonates are suction (or
vacuum) filtration and recrystallization. Suction filtration is used to separate the precipitate
product from the solvent. The solvent and air are forced through the Buchner or Hirsch funnel by
reduced pressure due to the vacuum.
Recrystallization is used because the product formed will still have some impurities in it.
In order to purify the compound, the compound is dissolved in a minimum amount of hot
solvent. This makes it easier to separate the impurities from the desired compound. When the
solution is cooled, the compound will crystallize and can be collected by filtering it from the
mother liquor.

Experimental:

Preparation of Cr(acac)3:
0.65g of CrCl36H2O and 10ml of distilled water were added to a 50-ml Erlenmeyer flask
with a magnetic stir bar. After the chromium dissolved, 2.5g of urea and 2.0ml of acetylacetone
were added. The flask was covered with a watch glass and clamped in position in a 500ml beaker
of boiling water on a magnetic-stirring hotplate. The solution was heated for 1 hour with stirring.
The flask was left to cool to room temperature. The product was collected through suction
filtration with a Hirsch funnel. The product was washed with three 1ml portions of water and
then placed in a desiccator along with the filter paper.

Preparation of Mn(acac)3:
1.0g of KMnO4 was dissolved in minimal volume of water. The water was slightly heated
in a hot-water bath and stirred with a glass rod. 4.5ml of acetylacetonate was added dropwise to
the solution with stirring. The solution was heated to just under the boiling point and kept at that
temperature for 5 minutes, then left to cool to room temperature. The solution was filtered and
washed with small amounts of 1:1 acetylacetone-water mix. The product was dissolved in
minimum amount of hot denatured ethanol for recrystallization. The same amount of distilled
water was added and the solution was placed in an ice bath. The crystals were filtered and then
dried by suction.

Preparation of Fe(acac)3:
3.0g of hydrated FeCl3 was dissolved in 3ml of distilled water with warming in a hot
water bath on a magnetic-stirring hotplate. 5ml of concentrated NH4OH solution was added
dropwise with stirring. The temperature was raised until the water was boiling. The solution was

heated at this temperature for 15 minutes and then left to cool to room temperature. The
precipitate was filtered and washed with water until there was no more chloride. The precipitate
and 6.15ml of acetylacetone were placed in a small flask. The flask was plugged with cotton
wool and heated in a hot-water bath for 40 minutes. The flask was then left to cool to room
temperature, and placed in an ice bath. The crystals were filtered and then recrystallized using
hot denatured ethanol. The product was filtered, washed with water, and then dried in a
desiccator along with the filter paper.

Preparation of Co(acac)3:
1.25g of CoCO3 and 10ml of acetylacetone were added to a 100ml flask and heated to
100C. The flask was removed from heat. 15ml of hydrogen peroxide was added dropwise over a
period of 10 minutes with stirring. The solution was cooled in an ice bath. The solution was
filtered and the product was dried at 110C.

Results and Observations:

Cr(acac)3 reaction:

+
urea
0.0416mol

H2O
water
0.5555mol

NH3 +
ammonia
0.0.832mol

acetylacetone
0.0195mol

3
+ CrCl36H2O
acac
chromium (III) chloride hexahydrate
0.0195mol
0.0024mol

2NH3
+
CO2
ammonia
carbon dioxide
0.0832mol
0.0416mol

+
acetylacetonate
0.0195mol

[NH4]+
ammonium
0.0195mol

+ 3HCl + 6H2O
Cr(acac)3
0.0024mol

Mn(acac)3 reaction:

3
acetylacetonate
0.0440mol

+ KMnO4
potassium permanganate
0.0063mol

+ KOH + H2O + O2
Mn(acac)3
0.0063mol

Fe(acac)3 reaction:

3
acetylacetonate
0.0599mol

FeCl3
iron (III) chloride
0.0123mol

+ 3HCl
Fe(acac)3
0.0123mol

Co(acac)3 reaction:

6
acetylacetonate
0.0974mol

+ 2CoCO3
cobalt (II) carbonate
0.0105mol

+ 4H2O + 2CO2
Co(acac)3
0.0105mol

Cr(acac)3 theoretical yield:

(0.0024mol) (349.32 g/mol) = 0.84g
Mn(acac)3 theoretical yield:
(0.0063mol) (352.26 g/mol) = 2.22g
Fe(acac)3 theoretical yield:
(0.0123mol) (353.17 g/mol) = 4.34g
Co(acac)3 theoretical yield:
(0.0105mol) (356.26 g/mol) = 3.74g
Discussion:
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The four metal acetylacetonates were successfully synthesized with what appears to be
some pretty decent yields. No characterization was performed yet so the percent yields were not
calculated yet. NMR, IR, UV-Vis, and maybe melting point, will be determined to characterize
the products soon and will determine if the data supports the structures of the acac complexes.
Also, the actual yield will be weighed and percent yield will be calculated.
The product formed from the Cr(acac)3 experiment appears to be a deep purple. The
product formed from the Mn(acac)3 experiment appears to be brown, and looks really muddy.
The product formed from the Fe(acac)3 experiment appears to be like a bright and bloody red,
and it reminds one of rust or Mars. The product formed from the Co(acac)3 experiment appears
to be dark green. All the products formed were also shiny, which is characteristic of metals.
A source of error in this experiment is the methods used to isolate the product from the
liquid. Every time the product is recrystallized and then suction filtrated and washed, there is loss
of product, leading to a smaller percent yield. The amount of recrystallizing, filtering, and
washing, depends on if purity of the compound or quantity of the compound produced is needed
more. Our group probably did not produce very pure acac complexes, but a nice amount of
product was yielded.
Another source of error was the magnetic-stirring hotplate. The hotplate used was old so
it was really bad at heating up water for the hot-water baths, and also the stirring function was
really bad too. The stir bar was not very effective and this may have affected our yield because
maybe the reaction was not complete due to lack of proper stirring.
One other source of error was during the Mn(acac)3 experiment. We were told to heat the
solution until it appeared muddy but our group was hesitant about how muddy our solution was.

So the solution was probably heated longer than needed and part of it probably dried up. This
would result in a lower percent yield.

Conclusion:
In conclusion, the acac complexes in this experiment were successfully synthesized, and
the products were very colorful and shiny. The Cr(acac)3 was purple, the Mn(acac)3 was brown,
the Fe(acac)3 was red, and the Co(acac)3 was green. The percent yields will be determined soon.

References:
(1) Zhang, Z.; Wong, C.; Fan, L. Study On Metal Acetylacetonates As Catalysts For Epoxy And
Anhydride Curing Reactions. PMSE Preprints 2002, 87, 382-383.
(2) Fdil, N.; Romane, A.; Allaoud, S.; Karim, A.; Castanet, Y.; Mortreux, A. Terpenic Olefin
Epoxidation Using Metals Acetylacetonates As Catalysts. Journal of Molecular Catalysis A:
Chemical 1996, 108, 15-21.
(3) Murugesan, N.; Sarkar, S. Catalyst Systems Derived From Transition Metal Acetylacetonates
For The Hydrogenation Of Aromatics. Indian Journal of Chemistry, Section A: Inorganic,
Physical, Theoretical & Analytical 1976, 14A, 107-111.
(4) CHY142 Organic Chemistry Laboratory Manual Fall 2014; Department of Chemistry &
Biology Ryerson University: Toronto, 2014; pp. 67-72.

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