In the Laboratory

Synthesis and Symmetry of Two Cobalt(III) Complexes

with Tetradentate Ligands
An Advanced Inorganic Chemistry Experiment
Mark McClure
Department of Chemistry and Physics, The University of North Carolina at Pembroke, Pembroke, NC 28372-1510;
mark.mcclure@uncp.edu

The study of symmetry in chemical compounds typically oxidation of CoCl2⋅6H2O with a stoichiometric quantity of the
falls under the realm of inorganic chemistry. However, when appropriate ligand and NaNO2; a yield of approximately 80% is
choosing examples of various point groups and explaining the typical if pure triethylenetetramine hydrate is used. The dichloro
relationship between symmetry and spectroscopy, many discus- compound [Co(tren)Cl2]Cl is prepared by stirring [Co(tren)
sions resort to organic molecules. In this laboratory students will (NO2)2]Cl with concentrated hydrochloric acid over a period
prepare two cobalt(III) complexes derived from two different of several days; a yield of approximately 65% is typical for this
tetradentate ligands, and the symmetries of these complexes will reaction. Lastly, the compound [Co(tren)(en)]Cl3 is prepared
be explored using 13C NMR spectroscopy. by refluxing [Co(tren)Cl2]Cl with a stoichiometric quantity
This experiment was designed for an advanced inorganic of ethylenediamine in methanol or ethanol; a yield of 65% is
chemistry course. It is typically the first lab performed in this typical for this reaction.
course and is intended to accompany lectures on symmetry
and group theory. The intended time frame is four weeks, three Hazards
weeks on synthesis and one week on NMR spectroscopy. A
number of important concepts are taught in this laboratory, All of the amines, as well as the 12 M HCl, are corrosive.
including the synthetic experience gained in preparing the com- Ethylenediamine fumes in moist air. Students should wear
plexes, an understanding of isomerism in chelate complexes, and gloves when handling these reagents. Sodium nitrite is potential
the spectroscopic experience gained in acquiring and interpret- carcinogen. Care should be taken to ensure that students do
ing the NMR spectra. not inadvertently mix the NaNO2 with the 12 M HCl, as this
releases toxic NO2 gas.
Experimental
Results and Discussion
The two ligands used in this study are triethylenetetramine
(trien) and tris(2-aminoethyl)amine (tren). Both of these Structural Illustrations of [Co(trien)X2]+ and [Co(tren)
reagents are inexpensive and are commercially available. The X2]+ are shown in Figure 1. (In actuality, three geometric isomers
complexes to be synthesized include [Co(trien)(NO2)2]Cl (1, are possible for [Co(trien)X2]+. However, under the conditions
2) [Co(tren)(NO2)2]Cl (3–5) and [Co(tren)(en)]Cl3, where en employed in this laboratory, only the symmetrical cis isomer
is ethlyenediamine. The dinitro compounds are prepared by air is formed.) The structures of these two series of complexes are
different and this is reflected in their 13C NMR spectra. The
compound [Co(trien)(NO2)2]Cl possesses a C2 axis that divides
the six carbon atoms into three sets of two equivalent atoms;
therefore a 13C NMR spectrum containing three resonances of
C1 roughly equal intensity is observed. The compound [Co(tren)
C4
(NO2)2]Cl possesses a mirror plane that contains one of the
C2 C2 C3 chelate arms and bisects the other two; this gives rise to a 13C
C3 C2
NMR spectrum containing two large and two small peaks. The
C1 compound [Co(tren)(en)]Cl3 gives rise 13C NMR spectrum
C3 C1
C2 similar to that of [Co(tren)(NO2)2]Cl but with two additional
resonances arising from the ethylenediamine.
C1
By comparing spectra, students should be able to assign all
of the resonances in [Co(tren)(NO2)2]Cl and partial assign-
C4 ments in [Co(trien)(NO2)2]Cl and [Co(tren)(en)]Cl3. The
C1 C2 C3
C2 C1 C2
N N compound [Co(trien)(NO2)2]Cl gives three peaks of roughly
C3 N X N N equal intensity at approximately 42.7 ppm, 55.5 ppm, and 57.5
Co C1
Co ppm. The compound [Co(tren)(NO2)2]Cl gives four signals
C3 N X X N
N X at 45.2 ppm (large), 45.3 ppm (small), 61.0 ppm (small) and
C2
C1 63.2 ppm (large). Lastly, the compound [Co(tren)(en)]Cl3
contains six signals at approximately 44.4 ppm (small) 45.0
Figure 1. Structural illustrations of [Co(trien)X2]+ (left) and [Co(tren) ppm (small), 45.5 ppm (small), 46.3 ppm (large), 61.9(small),
X2]+ (right) and 63.6 (large). Since the inclusion of ethylenediamine results

420 Journal of Chemical Education  •  Vol. 85  No. 3  March 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education 
 In the Laboratory

Table 1. Some Typical Chemical Shifts C1 carbon atoms. Similarly, for [Co(tren)(NO2)2]Cl the signals
Complex Chemical Shift (ppm) at 45.2 ppm and 45.3 ppm are assigned to the C3 and C1 carbon
atoms. In this case the relative heights of the signals also aid in
[Co(trien)(NO2)2]Cl 42.7 (C1)a
the assignments; the signal at 45.2 ppm is larger because it arises
55.5 (C3) as a result of two equivalent carbon atoms and is assigned to C1.
57.5 (C2) These data are summarized in Table 1.
[Co(tren)(NO2)2]Cl 45.2 (C1)
45.3 (C3)
Literature Cited
61.0 (C4) 1. Sargeson, A. M.; Searle, G. H. Inorg. Chem. 1965, 4, 45–52.
63.2 (C2) 2. Sargeson, A. M.; Searle, G. H. Inorg. Chem. 1966, 4, 787–796.
3. Toyota, E.; Yamamoto, Y.; Yamamoto, Y. Bull. Chem. Soc. Jpn.
[Co(tren)(en)]Cl3 44.4b
1988, 61, 3175–3180.
45.0b 4. Massoud, S. S.; Milburn, R. M. Inorg. Chim. Acta. 1988, 154,
45.5b 115–119.
46.3 (C1) 5. Massoud, S. S.; Milburn, R. M. Polyhedron. 1989, 8, 2389–
2394.
61.9 (C4)
63.6 (C2)
Supporting JCE Online Material
a Thecarbon positions are from Figure 1. b The C3 carbon is http://www.jce.divched.org/Journal/Issues/2008/Mar/abs420.html
indistinguishable from the ethylenediamine carbon atoms without
additional data. Abstract and keywords
Full text (PDF)
Links to cited JCE articles

in two additional signals in the region of 44–45 ppm, it can be Supplement

deduced that signals from carbon atoms adjacent to coordinated Student handouts icluding post-lab questions
NH2 groups fall within this region of the spectrum. Returning Instructor notes including the answers to the post-lab questions
to [Co(trien)(NO2)2]Cl, the signal at 42.7 can be assigned to the and the 13C NMR spectra

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 3  March 2008  •  Journal of Chemical Education 421