Synthesis, Spectroscopy, and Magnetic Susceptibility of Cobalt Complexes

Tilly Duffy with Rana El Ladki

November 21, 2019

Abstract

This experiment focuses on the coloring and chemical properties of cobalt complexes, which is

examined through use of Evans balances and absorption spectroscopy. It was found that ligand

Co(NO3)2•6H2O is paramagnetic, and high spin with three unpaired electrons and the ligand

Co(NH3)6Cl3 is diamagnetic. The complexes were also analyzed, and each respective crystal field

splitting energy was found.

Introduction

This experiment was conducted in order to analyze various cobalt (III) complexes through their

absorbance spectra and magnetic moments. This analysis will be used to determine the ligands

present, number of electrons present in the d orbital, and the spin of the electrons.

Experimental Methods

The experiment followed the procedure as given1 and no changes to the procedure were made.

Throughout the procedure the following chemicals were used: Columbus Chemical Industries

cobalt nitrate, Fisher Scientific Company 99.0% potassium oxalate, Sigma-Aldrich 99.0%

sodium nitrate, ChemPure Brand Chemicals 100% sodium bicarbonate, Aldrich Chemical

Company 99% hexaamminecobalt (III) chloride, Invitrogen UltraPure glycine, and J.T. Baker

99.0% sodium hydroxide. To test the qualities of the complexes in this experiment, a Johnson

Matthey Chemicals Limited Equipment Division Evans balance and an Ocean Optics

spectrometer were used.

Results

Throughout the experiment, the cobalt complexes’ absorbance spectra were taken in order to see

what wavelength of light each aqueous complex absorbs the most. First, the spectrum for

triglycinatocobalt(III), a pink-purple colored solution, was taken and is shown in Figure 1.

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Figure 1: The absorption spectrum for triglycinatocobalt(III).

Next, the absorption of trioxalatocobaltate(III), a light teal solution, was taken and is shown in

Figure 2.

Figure 2: The absorption spectrum for trioxalatocobaltate(III).

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Next, the spectrum was observed for hexanitrocobaltate(III), a rusty orange solution, is shown as

Figure 3 below.

Figure 3: The absorption spectrum for hexanitrocobaltate(III).

The spectrum for tricabonatocobaltate(III), a deep forest green solution, was found next and can

be found below as Figure 4.

Figure 4: The absorption spectrum for tricabonatocobaltate(III).

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The solution of hexaaquocobalt(III), a pale teal-blue solution, was observed next and the

absorbtion spectrum is represented in Figure 5.

Figure 5: The absorption spectrum for hexaaquocobalt(III).

Lastly, the absorption by hexaaminecobalt(III), a golden yellow solution, was observed and is

shown in Figure 6.

Figure 6: The absorption spectrum for hexaaminecobalt(III).

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Using the absorption data, the maximum wavelength of absorbed light for each solution was

found and used to determine the crystal field splitting energy (Do) for that complex, the

relationship of these data points and other characteristics for the complexes can be found in

Table 1.

Table 1: Cobalt(III) Complexes and the Corresponding Do, lmax, and Colors
Complex Do (kJ/mol) lmax (nm) Observed Color
triglycinatocobalt(III) 185.38 645.06 Deep Forest Green
trioxalatocobaltate(III) 198.91 601.18 Minty Teal-Green
hexanitrocobaltate(III) 252.07 474.40 Golden Yellow
tricabonatocobaltate(III) 255.26 468.47 Light Lavender
hexaaquocobalt(III) 294.61 405.91 Pale, Icy Teal-Blue
hexaaminecobalt(III) 305.08 391.98 Rusty Orange

For the cobalt complex Co(NO3)2•6H2O, the oxidation state for the cobalt was found to be +2

with seven electrons occupying the d-orbitals. The different spin patterns for the seven electrons

in the d-orbitals can be modeled by Figure 7, demonstrating the possible high spin and low spin

configurations. If the low spin configuration occurs, there will be one unpaired electron. If the

complex is in high spin, there will be three unpaired electrons present.

𝚫O 𝚫O

Low Spin High Spin

Figure 7: The low and high spin configurations for Co(NO3)2•6H2O.

In the complex Co(NH3)6Cl3, the cobalt atom was found to have an oxidation state of +3 and

contains six electrons in the d-orbitals. The two different spin configurations for the orbitals are

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modeled in Figure 8. In a low spin configuration, there will be no unpaired electrons. In a high

spin configuration, there will be four unpaired electrons present.

𝚫O 𝚫O

Low Spin High Spin

Figure 8: The low and high spin configurations for Co(NH3)6Cl3.

According to the magnetic susceptibility measurements, Co(NH3)6Cl3 produced a negative R

value when placed into the Evans balance, thus indicating that the substance is diamagnetic.

However, when the Co(NO3)2•6H2O was placed in the Evans balance, the R value was positive,

indicating that the substance is paramagnetic, using data from the balance, the effective magnetic

moment (µeff) for the substance was found to be 5.63 BM. By comparing the calculated µeff to the

known µeff values found in Table 31, it was determined that the complex has a high spin

configuration and contains 3 unpaired d-orbital electrons, as is modeled in Figure 7.

Discussion

Based on the data collected from this experiment, the crystal field splitting energy (Do) was

calculated. Using this information, it can be determined if the ligands contain relative weak or

strong fields which can be used create a spectrochemical series, ordering the ligands from weak

field to strong field:

CO3-2 < oxalate < NH3 < glycine < H2O < NO2-1

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The relative strength of the fields is determined by the magnitude of Do, which corresponds

directly to the impact that the ligand has on the d-orbitals. The determined series from the

experiment, however, is not entirely consistent with the provided series1, the placement for H2O

in the provided series indicates a weaker field than is present in NH3, which is different than seen

in the experiment. Not all of the ligands tested in the experiment are not present in the given

series. Based on the similarity in the chemical structures of CO3-2 and NO3-, it can be estimated

that their respective positions in the series should be similar, and the data proves to be consistent

with these estimations.

The observed colors of the solutions can be explained by their absorbance spectra that were

collected throughout the experiment and are shown in Figures 1-8. The absorption spectra should

indicate that the color opposite the observed color is being absorbed, so that the color that is not

absorbed is seen.

In this experiment it was found that Co(NO3)2•6H2O is a high spin complex, based on the

information given by the µeff value of 5.63 and the fact that the Evans Balance gave a positive

value, indicating paramagnetic characteristics. The Evans balance produced a negative value for

Co(NH3)6Cl3, indicating that the substance has diamagnetic qualities. Based on Figure 8, the

complex must be low spin, as that configuration contains no unpaired electrons (which contribute

to magnetism).

Conclusion

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In this experiment, using an Evans balance, it was determined that Co(NO3)2•6H2O is

paramagnetic with high spin and that Co(NH3)6Cl3 is diamagnetic. The colors of the cobalt(III)

complexes were also studied and compared to their absorption spectra, which corresponded and

explained their observed colors (for the most part).

References

1. Severin, K. Laboratory #9: Synthesis, Spectroscopy, and Magnetic Susceptibility of Cobalt

Complexes; Michigan State University; CEM 185H; 2019