Matt Prater

Ethylenediamine complexes of Chromium

Date Performed: 02/12/2015

Partner: Alyssa Brown

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Introduction
Transition metal complexes often have different colors depending on the specific ligands
surrounding the metal ion. For this experiment, tris(ethylenediamine)chromium(III) sulfate was
synthesized and then reacted to become tris(ethylenediamine)chromium(III) sulfate which was
partially decomposed to cis-dichlorobis(ethylenediamine)chromium(III) chloride. This is
important in order to see how the absorbance spectrum changes as the specific ligands change.
This is important to understanding ligand field theory and the significance of o which represents
the transition energy for electrons between the t2g and eg or the t2g and t2g* depending on the
specific environment involved. For the tris(ethylenediamine) complexes, the first set of orbitals
from point group theory represent the transition, but for the dichloro- complex, the latter set is
represented at chloro is capable of being a pi donor ligand.
Procedure
6.0033 g of Cr2(SO4)3*H2O (non-stoichiometric) was placed in a test tube and allowed to
dry in an oven for 3 days. On the third day, the green solid was removed from the test tube and
then crushed into a fine powder with a pestle and mortar. The power was placed back in the test
tube and in the oven for another 24 hours. 10 mL ethylenediamine (99%) was added to the test
tube and the test tube was placed in a boiling water bath for 3 hours to reflux. The final mixture
was placed in the oven again to evaporate the excess ethylenediamine, 2.1 g of an orange solid
resulted (tris(ethylenediamine)chromium(III) sulfate). This solid was taken and added to a 60 C
solution of 2 M HCl and filtered. The filtrate was added to a solution of 5 mL concentrated HCl
and 8 mL ethanol and was cooled in an ice bath with stirring. Yellow needles began to form but
due to time constraints, tris(ethylenediamine)chromium(III) chloride hydrate was not isolated.
0.1000 g NH4Cl was added to the solution and there was a significant amount of solvent,
therefore it was boiled on the hot plate and it turned red. The solutions were ran on the UV-vis to
verify that the desired product had been formed.1

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Data

Cr(en)3Cl3
0.03
0.03
0.02
Absorbance

0.02
0.01
0.01
0
300 350 400 450 500 550 600 650 700
Wavelength (nm)

Figure 1: Absorbance spectrum of tris(ethylenediamine)chromium(III) chloride.

dichlorobis(ethylenediamine)chromium(III) chloride
0.03
0.02
0.02
Axis Title 0.01
0.01
0
300 350 400 450 500 550 600 650 700
Wavelength (nm)

Figure 2: Absorbance spectrum of dichlorobis(ethylenediamine)chromium(III) chloride

Material

Amount

Initial Cr2(SO4)3 * H2O

Final anhydrous Cr2(SO4)3
99% Ethylenediamine
Initial [Cr(en)3]2(SO4)3
Mass of [Cr(en)3]3+ recrystallized
Ending [Cr(en)3]Cl3 mass
Ending cis-[CrCl2(en)2]Cl

6.0033 g
4.9801 g
10 mL
1.1355 g
0.1030 g
In aqueous solution
In aqueous solution

Discussion

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The ethylenediamine complexes of chromium can be more difficult to prepare than it

would seem on paper. This is because the above procedure was attempted more than once in
order to get the desired product. The first time was not successful as a solid black product was
formed in the test tube during the pseudo reflux. that seems insoluble in everything that has been
tried. There was a small amount of orange product that didnt result in more than a few crystals
of end product. The second time also formed a dense insoluble black solid, but less was formed
and more of the desired product was produced in order to go on to the next step. The reflux step
should have been done in an erlenmyer flask as extracting the solid from the test tube was
difficult. The laboratory procedure does say that the reflux should take about 1.5 hours, waiting
until all of the liquid (ethylenediamine) has evaporated. This did not occur in 1.5 hours, perhaps
due to the lower air pressure in Cedar City; therefore, the solution was allowed to reflux for 4
hours the first time and the liquid had still not evaporated. That long of a reflux may have caused
the formation of that solid black byproduct. The spectra show that the dichloro was found in the
final product due to the broadening of the peaks above (pi-donor ligand).
Conclusion
From the above discussion, it appears reasonable to conclude that it is possible to reflux
these compounds too long as they will undergo some kind of thermal decomposition into an
unknown compound that is insoluble. It is also a better idea to perform the reflux in a flask that is
larger that makes product removal easier. The broadening of the peaks also shows that the
desired product was formed.
Questions
1. Write the structures for both the cis and trans form of dichlorobis(ethylenediamine)chromium(III) chloride.

Trans:

cis:

2. How many unpaired electrons would you expect for the product prepared.
3, it is a d3 system.

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3. How else besides conductivity might you determine how many of the chlorines in the
final product are ionic.
The chorines could be displaced by fluorine gas (F2) which would become fluorides and
the chlorides would become Cl2 and then a chlorine NMR could be taken.
4. How can infrared spectroscopy help in characterizing these compounds?
The fingerprint region would have a very strong peak around 700 cm-1.
5. Does the final poduct have a plane or center of symmetry?
The trans product has both, but the cis does not have either.
6. What about the tris(ethylenediamine)chromium(III) sulfate? (part 2 of q 5)
It has a center of symmetry but not a plane of symmetry.

References

(1)
Experimental Methods in Inorganic Chemistry: John Tanaka, Steven L. Suib:
9780138419097: Amazon.com: Books, 2015.