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Synthesis and Characterization of the Bis Complexes of Cobalt ()

with Iminodiacetic Acid
Shu-juan LIU
Abstract: The two geometrical isomers of K[Co(IDA)2] have been prepared and characterized
through UV-VIS spectra, ICP-AES, and Cyclic Voltammetry. The Co() complexes are octahedral
structure. The brown isomer is in the cis configuration and the violet one is in the trans
configuration. The cyclic voltammograms are also analyzed.

Key words: Cobalt() complexes, iminodiacetic acid

1. Introduction
Cobalt () and iminodiacetic acid (IDA) can form the ML6 complex [Co(IDA)2] -.The
iminodiacetic acid ligand with the donor atom array ONO can occupy three of the octahedral sites
around the central ion Co ()[1]. In the case of [Co(IDA)2] - three geometrical isomers can be
expected: cis, fac-trans and mer-trans (Figure1) . However, due to spacial strain , the isomer (3) has
higher energy and is instable. So the trans isomer prefers to take a facial configuration (fac) rather
than a meridional one in most synthetic routes. And it has been confirmed by NMR.

(1)cis

(2)mer-trans

(3)fac-trans

Figure1 The Geometrical Isomers of [Co(IDA)2] In this paper, cis-[Co(IDA)2] - and fac-trans-[Co(IDA)2] - have been prepared. The
stereochemistry of [Co(IDA)2] - was investigated through UV-VIS spectra, ICP-AES, and Cyclic
Voltammetry.

2. Experiment
2.1 Preparation of the violet isomer
To the solution of 0.8g of KOH in 4 mL water, add 1g iminodiacetic acid and then 0.8g
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CoCl2 6H2O.Stir to make them dissolved. Put the solution in cool water bath at 10-12, and then
add 2.5 mL 15% hydrogen peroxide solution under stirring in 2-3 min. Stir the purple mixture for
2.5 h at 10-12 in water bath. Filter the solution in a Buchner funnel, and wash the products
successively with 2 mL 95% ethanol and 2 mL acetone. Allow the product to air dry. Yield: 0.68g
(56.2%) of violet isomer.

2.2 Preparation of the brown isomer

To the solution of 0.8g of KOH in 8 mL water, add 1g iminodiacetic acid and then 0.8g
CoCl26H2O. Stir to make them dissolved. Heat the solution in water bath to 80, and then add 0.5
mL 30% hydrogen peroxide solution under stirring. Heat the mixture in water bath for 45 min at
80. Allow the solution to cool for 2.5 h. Filter the mixture in a Buchner funnel, and wash the
products successively with 2 mL 95% ethanol and 2 mL acetone. Allow the product to air dry. Yield:
0.53g (43.8%) of brown isomer.

2.3 Ion exchange separation of the isomers

The resin used is chloride strong basic anion-exchange resin. Elute the column with distilled
water until no Cl- can be detected. When the liquid level is tangent with the resin level, pour about
3mL mother liquor of the brown isomer into the column, and keep the current velocity at 10-15 s
per drop. When the liquid level is tangent with the resin level again, elute the resin with 3 mL water.
Then elute the resin with 0.1 mol/L NaCl solution until two color bands appeared on the column:
brown (first) and violet (second). Collect about 3 mL eluate of each band.

3. Result and Discussion

3.1 Ion-exchange separation
When K[Co(IDA)2] solution flows through the chloride strong basic anion-exchange resin, the
Cl in the solid phase exchanged with the [Co(IDA)2]- in the liquid phase. The resin can soon reach
exchange equilibrium under certain temperature.
~N+Cl- [Co(IDA)2]~N+[Co(IDA)2]- ClThough the cis and trans isomers have the same charge, they have differrent affinity with the
resin, due to different polarity. Isomer with higher polarity has stronger affinity with the resin, so
that it can be absorbed more easily. When NaCl solution elutes the resin absorbed both of the
isomers, the following reaction will occur between the solid phase and liquid phase.
~N+[Co(IDA)2]- Cl~N+Cl- [Co(IDA)2]So the isomer which has weaker affinity must be eluted earlier than the other one, and distinct
color bands will appear on the column. Because the brown isomer is eluted first, it has weaker
affinity and lower polarity. According to the molecule models, the fac-trans isomers have lower
polarity. So it can be said that the brown products are in the fac-trans configuration, and the violet
ones are in the cis configuration.
-

3.2 UV-Vis absorption spectra

The UV-Vis absorption spectra of cis and trans isomers are shown in Figure 2 and the
absorption data are summarized in Table 1. From the table we can see that all the three complexes
have the maxima of absorption at about 550nm, which means that they have similar geometrical
configurations. Because Na[Co(EDTA)] is octahedral structure, it is certain that K[Co(IDA)2] is
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octahedral structure too.
The two spin-allowed transitions in a low-spin d6 system in an octahedral crystal field are
1
1
1
A1g
T1g (band, low frequency)and 1A1g
T2g (band, high frequency)in order of
[2]
increasing energy . As we scan from 400nm to 700nm, band are not shown in the figure bellow.
With further decreasing of molecular symmetry, further splitting is expected. According to the
crystal field theory, the bandof the trans isomer (brown) splits into two bands, while the band
of the cis isomer (violet) is asymmetric or appears as a shoulder peak. Our results confirm these
facts. And we can further confirm that the violet products are in the cis configuration.
0.8

0.6

0.4

0.2

0.0
400

450

500

550

600

650

700

(nm)

Figure 2 The UV-Vis Absorption Spectra of Cis and Trans Isomers

Solid line: brown eluate
Dot line: violet eluate
Dash dot line: 0.05 mol/L Na[Co(EDTA)] solution(Dissolve 0.1189g
CoCl26H2O in 10 mL water. Add 0.1862g EDTA and then 2 drop of H2O2
solution. Heat the solution to remove the unreacted H2O2 and then dilute it
to100 mL.)

Table 1 Band Maxima of The UV-Vis Absorption Spectra of Cis and Trans Isomers
complex

(nm)
606
495
559
534

Brown isomer
Violet isomer
Na[Co(EDTA)]

0.0820
0.3226
0.3138
0.6773

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3.3 ICP-AES
The result of ICP-AES of the two products is listed in table 2. The contents of K and Co are
lower than the theoretical amount. That is because the products obtained have some impurities. As
the brown isomer is synthesized with no stirring, the amount of impurities is less than the violet one.
Because the isomers have the same molecular formula, the contents of K and Co are almost the
same.

Table 2 Contents of K and Co

Complex
K%
Co%

Brown isomer
8.78
11.79

Violet isomer
8.76
11.73

3.4 Cyclic Voltammetry

The cyclic voltammograms (scanned from +0.4 v to -1.2 v) of K[Co(IDA)2] has only a
reduction peak, which indicates that the electrode reaction is irreversible. That means Co()is
more stable than Co() in K[Co(IDA)2].
The peak potential of brown (trans) isomer is morenegative than the violet (cis) one at the
same scanning rate. It indicates that the trans isomer, which has a more symmetrical structure, is
more stable than the cis one.
The peak current of the brown isomer is larger than the violet one at the same scanning rate.
According to the Randles-Sevcik equation (25), the peak current is concerned with electrode area
(A), diffusion coefficient (D) , scanning rate (v) , concentration of the electro active material (c) . So
we can decide that the diffusion coefficients of the two isomers are different, because the else of the
factors are same in the experiment. The trans isomer has larger diffusion coefficient than the cis
one.

4. Conclusion
Through the synthesis and characterization of the two geometrical isomers of K[Co(IDA)2], I
know more about the Co() complex. And I also have a further apprehension of different
characterization methods.

Reference
[1] Tibor J. Sabo.Journal of Huanhai Institute of Technology,10,28-33(2001).
[2] Dean W. Cooke.ACS.5,1141-1145(1966).