Journal of Laboratory Chemical Education 2018, 6(5): 159-163

DOI: 10.5923/j.jlce.20180605.04

Geometric Isomerism in Octahedral Complexes:

Synthesis, Characterization, and Reaction of
Trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride
Jocelyn Pineda Lanorio1,*, Jerry Gomez Lanorio2

1
Department of Chemistry, Illinois College, Jacksonville, IL, USA
2
Division of Mathematics, Science and Physical Education, Lincoln College, Lincoln, IL, USA

Abstract The synthesis of the coordination complex trans-dichlorobis(ethylenediamine)cobalt(III) chloride is a classic

experiment and can provide an opportunity for inclusion of diverse concepts if additional activities are incorporated. This
laboratory experiment outlines the use of modern instrumentation such as UV-Vis spectrophotometer for thermal ligand
substitution monitoring, and the magnetic susceptibility balance for confirmation of the electron configuration of the
cobalt(III) center in trans-dichlorobis(ethylenediamine)cobalt(III) chloride.
Keywords Geometric isomerism, Octahedral cobalt(III) complexes, Aquation, Ligand substitution, Oxidation-reduction

[Co(en)2Cl(H2O)]Cl2, is purple in color and has cis geometry.

1. Introduction [2]
This laboratory experiment introduces inorganic
chemistry undergraduate students to the synthesis and
characterization of coordination compounds, geometric
isomerism, ligand substitution, magnetism and dn electron
configuration, and the use of UV-Vis spectroscopy for
monitoring reaction progress. It also provides students the
opportunity to see the energy and stability difference of
geometric isomers.
This is a two-week laboratory experiment. The synthesis
of trans complex will be done during the first meeting, then
Trans cis
characterization of trans-[Co(en)2Cl2]Cl and aquation will
Figure 1. Example of geometric isomers with octahedral geometry be on the second week. Upper level undergraduate students
Disubstituted planar and octahedral complexes exhibit can be asked to calculate the rate constant for the ligand
both cis and trans stereochemistry. Figure 1 shows an exchange reaction of water for a chloride ion in
example of octahedral geometric isomers. Octahedral trans-dichlorobis(ethylenediamine)cobalt(III) ion, with the
cobalt(III) complexes that are low-spin d6 configuration are assumption of a pseudo-first order rate law. [3]
diamagnetic and considered stable, [1] having a filled t2g
subshell. Due to the relative inertness of octahedral
cobalt(III) metal centers, [1] their ligand substitution and
2. Experimental Section
isomerization reactions are slow compared to the complexes Customized side arm test tubes (Figure 2) were fabricated
of many other transition metals. This allows us to monitor at Illinois College Department of Chemistry by the
the substitution of chloride by water in the green laboratory manager, Andy Stice. Alternatively, these can be
trans-dichlorobis(ethylenediamine)cobalt(III) chloride, purchased from several manufacturers such as Eisco labs,
trans-[Co(en)2Cl2]Cl complex. The aquation product, Haines Educational, and OnlineScienceMall, among others.
Reagents were obtained from commercial sources and used
* Corresponding author:
as received. Thermal monitoring of the ligand substitution
jocelyn.lanorio@ic.edu (Jocelyn Pineda Lanorio)
Published online at http://journal.sapub.org/jlce
was carried out using Cary-60 UV-Vis spectrophotometer.
Copyright © 2018 The Author(s). Published by Scientific & Academic Publishing The cuvette is immersed into hot water bath and transferred
This work is licensed under the Creative Commons Attribution International every 2 minutes to the UV-Vis spectrophotometer for a
License (CC BY). http://creativecommons.org/licenses/by/4.0/ wavelength scan.
160 Jocelyn Pineda Lanorio et al.: Geometric Isomerism in Octahedral Complexes: Synthesis,
Characterization, and Reaction of Trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride

Students were provided with an experimental handout and 2.2. Characterization

asked to answer the following prelab questions: The green trans-[Co(en)2Cl2]Cl compound was weighed,
1) Draw the structure of the complexes, and the percentage yield was obtained. The product was
trans-[Co(en)2Cl2]Cl and cis-[Co(en)2Cl(H2O)]Cl2. characterized by IR and UV-Vis spectroscopy.
2) Balance the oxidation-reduction reaction involved in The IR spectrum of the product, Figure 5, was acquired
the synthesis of trans-[Co(en)2Cl2]Cl. using the Varian 640-IR FT-IR spectrophotometer. The
Co2+ + H+ + H2O2  Co3+ + H2O molar extinction coefficient of trans-[Co(en)2Cl2]Cl was
Which species is the oxidizing agent? Which is the determined by preparing 5 mL aqueous solutions of 0.02,
reducing agent? 0.04, 0.08, 0.12, 0.16 M trans-[Co(en)2Cl2]Cl. The UV-Vis
spectra were obtained from 700 to 300 nm using the
Cary-60 UV-Vis spectrophotometer.
The magnetic moments of trans-[Co(en)2Cl2]Cl and the
starting material, CoCl2·(H2O)6, were determined by the
Gouy technique. The calibration constant of the instrument
was determined using mercury tetrathiocyanatocobaltate(II)
as the standard reference material. Students were introduced
and provided with the formula of the magnetic moment
(eff), as well as diamagnetic corrections for the ligands, [5]
for positive reading (paramagnetic case).

Figure 2. Customized side arm test tubes

2.1. Synthesis of
Trans-Dichlorobis(ethylenediamine)co-balt(III)
Chloride
A modified procedure from Szafran, Pike, and Singh [4]
for the synthesis of trans-dichlorobis(ethylenediamine)
cobalt (III) chloride, trans-[Co(en)2Cl2]Cl, was performed.
CoCl2.6H2O (300 mg, 1.26 mmol), water (2.5 mL), and 10%
ethylenediamine (1 mL) were added to the side arm test tube.
Dropwise addition of 0.300 mL of a 30% H2O2 solution was
then done, followed with dropwise addition of 0.600 mL of
concentrated HCl. A Pasteur pipet was inserted through a
rubber stopper with a drill hole, to serve as air inlet, Figure 3.
The test tube was then clamped in a hot water bath. Air was Figure 3. A Pasteur pipet was inserted through a rubber stopper with a drill
drawn slowly and continuously through the solution by hole, to serve as air inlet
connecting the side arm of the test tube to a vacuum source
(aspirator or hood vacuum) by way of a water trap using
appropriate tubing, Figure 4. The reaction was heated and
oxidized until green crystals were apparent. Additional water
should be added if the test tube is almost dry but has no
formation of green crystals. The mixture was cooled in ice
bath and then filtered by suction. The green crystals were
washed twice with 2-mL portions of cold methanol, and then
two 2-mL portions of cold diethyl ether. The filtrate that
contains the HCl co-solvate (additional crystalline product)
was discarded. The crystals were placed on a small watch
glass and heated in an oven at 110C until the next lab
session.
The balanced chemical equation for the synthesis of
trans-[Co(en)2Cl2]Cl is as follows:
2CoCl2·(H2O)6 + H2O2 + 2 HCl + 4 en  Figure 4. Microscale synthesis of trans-[Co(en)2Cl2]Cl complex using a
2 [Co(en)2Cl2]Cl + 14 H2O test tube with side arm attached to water-trap then vacuum source
 Journal of Laboratory Chemical Education 2018, 6(5): 159-163 161

2.3. Aquation of trans-[Co(en)2Cl2]Cl: Synthesis of resulting solution contains the cis-[Co(en)2Cl(H2O)]Cl2

Cis-Dichlorobis(ethylenediamine)cobalt(III) complex. The UV-Vis spectra display the absorption
Chloride maxima for trans-[Co(en)2Cl2]Cl and
UV-Vis spectrophotometer was used to observe the cis-[Co(en)2Cl(H2O)]Cl2, Figure 6.
isomerization/aquation process at 80C. The aquation reaction [6] involved is:
A glass cuvette was filled with a few milliliters of 0.016 M [Co(en)2Cl2]+ + H2O  [Co(en)2Cl(H2O)]2+ + Cl
aqueous trans-[Co(en)2Cl2]Cl solution. The cuvette was Students can be asked to completely evaporate the water
placed in a hot water bath then transferred to the UV-Vis from the aqueous purple solution using the roto-evaporator.
sample holder for wavelength scan from 700 to 300 nm, in This step will show students the more stable isomer in the
2-minute intervals. Chloride substitution with water is solid state.
complete once the solution turns purple permanently. The

Figure 5. IR spectrum of trans-[Co(en)2Cl2]Cl

Figure 6. UV-Vis spectra for the water substitution of chloride in trans-[Co(en)2Cl2]Cl

162 Jocelyn Pineda Lanorio et al.: Geometric Isomerism in Octahedral Complexes: Synthesis,
Characterization, and Reaction of Trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride

3. Results and Discussion negative, indicating the diamagnetic nature of the cobalt
center.
The set-up for the microscale synthesis of Evaporation, using a roto-evaporator, of the resulting
trans-[Co(en)2Cl2]Cl is shown in Figure 4. The initial and aqueous solution of cis-[Co(en)2Cl(H2O)]Cl2 yielded green
final colors of the mixture are shown in Figure 7. The final crystals.
product trans-[Co(en)2Cl2]Cl obtained after filtration during
the first lab meeting is shown in Figure 8. Typical student
yields for the synthesis of trans-[Co(en)2Cl2]Cl were in the
range of 45 to 50%.

Figure 9. Cis-[Co(en)2Cl(H2O)]Cl2 complex

Figure 7. Initial and final color of the mixture

Figure 10. Negative reading from magnetic susceptibility balance for the
trans-[Co(en)2Cl2]Cl complex

4. Conclusions
This lab was successfully carried out by CH 332
Advanced Inorganic students in the Fall 2017 at Illinois
College. The negative magnetic moment confirmed the
Figure 8. Trans-[Co(en)2Cl2]Cl successful oxidation of Co(II) to Co(III), and the d6 electron
configuration of the cobalt(III) center. The IR spectrum
The IR spectrum of solid trans-[Co(en)2Cl2]Cl (Figure 5)
showed the NH2 vibrational modes of the coordinated
showed two absorption bands in the 3200 cm-1 region
ethylenediamine ligand. The maximum absorption
corresponding to the NH2 stretching vibrations of the
wavelengths obtained from UV-Vis spectral analysis of
coordinated ethylenediamine; whereas, the absorption bands
trans-[Co(en)2Cl2]Cl and cis-[Co(en)2Cl(H2O)]Cl2 are 618
in the 1635 to 1578 cm-1 can be assigned to the NH2
nm and 509 nm, respectively. Students realized the
deformation frequencies.
importance of further use of modern instrumentation in
Absorbance, at the maximum wavelength of 618 nm, as a
monitoring reaction and determination of kinetic parameters,
function of concentration was plotted to determine the
as noted in their lab reports.
molar extinction coefficient (= 37.00 M-1cm-1).
The formation of cis-[Co(en)2Cl(H2O)]Cl2 was monitored
at 80C over time by UV-Visible spectroscopy in water,
which shows the disappearance of the peak at 618 nm and the
ACKNOWLEDGEMENTS
appearance of another peak at 509 nm, Figure 6. The initial The experimental data presented in this work was obtained
green aqueous solution of trans-[Co(en)2Cl2]Cl turned by Chan Myae Lin Latt and the CH 332 Advanced Inorganic
purple and was converted to cis-[Co(en)2Cl(H2O)]Cl2, Chemistry students, with the equipment and facilities of
Figure 9. Illinois College Department of Chemistry.
The magnetic susceptibility balance reading of
trans-[Co(en)2Cl2]Cl (Figure 10) was determined to be
 Journal of Laboratory Chemical Education 2018, 6(5): 159-163 163

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