Synthesis of Co(dinosar)Br

3
from tris(ethylenediamine)-
cobalt(III)
Walmiria Lima da Costa
10
th
March, 2014
Abstract
The macrobycyclic complex Co(dinosar)3+ is a widely studied complex
between undergraduate students, once that it has safe and inexpensive
synthesis and allows large comprehension of coordination chemistry, if correctly
studied. In this experiment, this compound was synthesized by an organic
template reaction within Co(en)
3+
, which is inert. The characterization of the
complex obtained was made throughout Infrared, Visible region and 1H NMR
spectra, and it was found on the evidences of the formation the complex.
Introduction
Metals can be found on nature in various forms. One of them is in the
form of metal complexes, a field that has been widely studied in recent
decades. Among the reasons why scientists are so interested in metal
complexes, especially in regards to metal complex with macrocyclic ligands, is
the fact that this type of chemical compound can be found in various routes of
metabolism of living beings, working mainly as enzymes and/or catalysts.
Another important factor that stimulates the study of this type of chemical
compound is the fact that metal complexes with macrocyclic ligands are, on
their most part, chemically stable and have a distinct three-dimensional
structure, which is very difficult to predict and that may exhibit absorption
properties, for example.
In the study of inorganic chemistry, a safe and inexpensive experiment
which brings research related to synthesis of macrocyclic complexes is the
experiment dinosar. Or synthesis of Co(dinosaur)
3+
, and dinosar equals to 1,8-
dinitro-3,6,10,13,16,19-hexaazabicyclo-(6.6.6)icosane). In this experiment, the
compound is obtained through a stepwise fashion process, from Co(en)
3
3+
. A
suggested pathway has been shown below:






Experimental
In a 150mL conical flask, 1.25g of Co(en)
3
Br
3
and 0.75g of Na
2
Co
3
were
dissolved in 40 ml of water, flowed by the addition of nitromethane (2.5mL) and
37% aqueous formaldehyde. After a quick mix stir to mix the reagents, the
solution was placed in a waterbath and maintained at 35-40C for 1 hour.
After a short time, it could be observed that the solution changed its colour from
yellow to a dark brown. Also, after more or less one hour, an appreciable
amount of yellow crystals started to be formed. The solution was briefly and
occasionally stirred with a glass rod, to help induce crystallisation.
After the waterbath, the solution was immediately cooled to ~5C in an
ice bath. The crystals were then collected on a sintered frit under suction. The
collected solid was dissolved on the frit using portions of hot dilute acetic acid
1M, in a total of ~15mL. The hot yellow filtrate was then treated immediately
with concentrated HBr (7.5mL). In this stage, a copious fine yellow crystalline
precipitate could be observed. When it was in room temperature, the precipitate
was collected on a frit under suction, washed with cold 1:1 methanol: water,
methanol, then ether, and dried with suction.
The starting material and the final complex were recorded using the Cary
spectrophotometer to visible spectra in the range 300-600 nm and the infrared
spectra by Nujol mull on NaCl disks in the range 2000-600 cm-1.
Results and Discussion
The synthesis occurred according to the simplified expression:
Co(en)
3
Br
3
+ 2 CH
2
NO
2
Co(dinosar)
3+

Having the molecular weight of the starting material as 478,945 g/mol
and product as 673,091 g/mol, and knowing that it was used 1,25g of the
starting material, it possible to conclude, throughout theoretical yield
calculations, that it is expected 1,757g of product to have an 100% yield.
However, during the practise, it was obtained 0,5g of product, the same as
28,470% yield. This value can be compared with the obtained by Harrowfield
and team (1985), who had a yield of 55%, which is considerable good to an
inorganic synthesis.
To characterization of the starting material and final product, it was taken
visible and infrared spectra, as well as analyses of the
1
H NMR spectra for both
of them (all these spectra are attached at the end of this report). For the visible
spectra, it was used samples with molar concentrations of 2,714mM and
1,486mM for starting material and product, respectively. Knowing this and
having knowledge about the Beer-Lambert law (A= c.l), it is possible to
measure the molar absorption coefficient values to both starting material and
Co(dinosar)
3+
, where c is concentration of the samples and l is the length of
solution the light passes though, which is given as 1 cm for the experiment
done. The obtained results are shown on table 1.
Table 1: Visible spectra data for both starting material and final product.

max
Absorbance Concentration
max

Co(en)
3
Br
3
466.5 0.295 2.714 mM 108.7M
-1
cm
-1

Co(en)
3
Br
3
331.0 0.344 2.714 mM 126.9 M
-1
cm
-1

Co(dinosar)
3+
473.0 0.258 1.486 mM 173.6 M
-1
cm
-1

Co(dinosar)
3+
342.3 0.348 1.486 mM 234.2 M
-1
cm
-1


The values obtained for
max
for both samples are similar to that found by
Harrowfield and team (1985), who did the same experiment and had absorption
maxima in the visible region at 475 nm and 342 nm for Co(en)
3
Br
3
and at 466
nm and 338 nm for Co(dinosar)
3+
. These absorption are typical of an octahedral
compound and the values of
max
are indicator of d d transitions within orbital
in both compounds.
While the spectra in the visible region are similar to the start material and
final product, the same cannot be observed in the infrared spectra. There are
peaks present in both spectra, however, the Co(dinosar)
3+
has fingerprints
which are characteristics of its nitro group ( -NO
2
). The signals at 1351.60 and
1556.76 cm
-1
in the spectra of the final product are result of the symmetric and
asymmetric stretching of the nitro group , which was not present in the starting
material. Similar results were found for Carriazo and team (2013), who got
peaks at 1345 and 1560 cm
-1
, attributed to symmetrical and asymmetrical
stretching vibrations, respectively, of nitro (NO
2
) groups in the [Co(diNOsar)]3+
complex which they synthesized.
Analysing the
1
H NMR spectra for both complexes, it is possible to
observe that there are more peaks in the spectra of the final product. It means
that there are less equal hydrogen on this than in the starting complex.
Conclusions
The synthesis here described did not have a good yield, however it was
efficient, according to the Infrared and visible spectra, as well as what can be
observed in the
1
H NMR spectra. The first one has shown clear signs of a
presence of nitro groups in the final product, which is coherent with the
supposed mechanism. The visible spectra showed significant changes from the
starting to the final material, as an evidence of the changes which occurred in
the complex. The same was observed to the
1
H NMR spectra.
References
Harrowfield, Jack M., Lawrance, Geoffrey A., Sargeson, Alan M. Chem. Ed.,
1985. 62, 804-806.
Carriazo, Jos G., Montoya-Gonzalez, Efran A., Vanoy-Villamil, Michael N.
Qum. Nova [online]. 2013. 36, 1318-1322.
Qin, Chang-Jin, James, Lloyd, Chartres, Jy D., Alcock, Leighton J., Davis,
Kimberley J., Willis, Anthony C., Sargeson, Alan M., Bernhardt, Paul V., Ralph,
Stephen F. Inorg. Chem. 2011, 50, 91319140.