LINKAGE ISOMERS:

SYNTHESIS AND
CHARACTERIZATION OF
[CO(NH3)5ONO]CL2 AND
[CO(NH3)5NO2]CL2
Experiment 2.4

JUNE 3, 2022
KGASU MOSA
202112103
AIM
1- To prepare the linkage isomers: Nitritopentaamminecobalt (III) chloride and Nitropentaamminecobalt
(III) chloride
2- To distinguish between the nitro- and nitrito-complexes experimentally

INTRODUCTION
In this Linkage Isomers: Synthesis and Characterization of [Co(NH3)5ONO]Cl2 and [Co(NH3)5NO2]Cl2
experiment, There will be synthesize of two cobalt coordination complexes, which are, [Co (NH3)5(NO2)]Cl2 and
[Co(NH3)5(ONO)]Cl2, and investigate linkage isomerism. The linkage isomerism which involves ligands that are
capable of bonding through one type of atom in one situation and another type of atom in a different situation. The
nitrite ligand can link to metals through the N atom (“nitro” complexes) or the O atom (“nitrito” complexes) (see
below). The nitrito isomer is less stable and can be converted to the nitro isomer slowly by standing at room
temperature, or quickly by heating or addition of HCl to a solution containing the nitrito compound.

The preparation of Co (III) pentaammine complexes is carried out most conveniently starting from CoCl2·6H2O.
The first step in the syntheses of these complexes requires oxidation to convert the metal from the +2 to the +3
oxidation state. The oxidation reaction is best carried out using concentrated H2O2 in basic ammonia solution.
Hydrogen peroxide as an oxidizing agent generates only OH– as reduced product, and the presence of ammonia
guarantees that the Co3+ will be stabilized immediately by formation of amine complex(es). (The Co3+ ion is not
stable in aqueous media since it forms the strongly oxidizing hexaaqua complex.

PROCEDURE
For the first part of our experiment, I started off by part one; the following are the steps that I took to synthesize
chloropentaamminecobalt (III) chloride, [Co (NH3)5Cl] Cl2.

PART I: CHLOROPENTAAMMINECOBALT (III) CHLORIDE, [CO (NH3)5CL]CL2

5.001g of ammonium chloride NH4Cl was measured in the weighting instrument which was then transferred in a
250 mL Erlenmeyer flask which contained 30 mL of concentrated aqueous ammonia and magnetic stir bar. The
solution was stirred with magnetic stir bar, then 9.993 g of cobalt (II) chloride hexahydrate was added to the
solution. The stirring continued while 8 mL of a 30% H2O2 solution was slowly added to the main solution. As the
reaction continued, 30 mL of concentrated HCl was slowly added to that solution. The solution was heated using a
hot plate. The was a close control of temperature to be of about 85°C for 20 minutes. The solution was not allowed
to boil. The solution was slightly heated and then after the heating process it was placed in an ice water bath for
cooling. The crystalline product was isolated by suction filtration. The product was then washed with a small
amount of ice-cold water 14 ml of ice-cold water was used to wash the product. The total volume of the wash
should not exceed 15 mL. The washing process contained where 15 mL of cold 6M HCl was used to wash the
crystalline product. The product was placed in a drying oven for 15 minutes and then the product was weighed for
the purpose of getting the percent yield. Then the sample was Allowed to dry. Before it was submitted for IR
spectrum and the UV-Vis spectrum.

PART II: PENTAAMMINENITRITOCOBALT ( III) CHLORIDE, [CO (NH3)5ONO] CL2

A solution of 8.0 mL of concentrated aqueous ammonia (NH4OH) in 80 mL of distilled water was heated, while
heating and stirring, add 5.006 g of ‘dry’ [Co (NH3)5Cl] Cl2 was slowly added to the solution. The solution
Continued heating, below boiling point, and stirring also continued until the product was all dissolved. The presence
of a dark brown to black precipitate of cobalt oxide was then observed, it was then filtered off. Cool the solution, in
an ice bath, to about 10 °C. The titration of the solution with 2M HCl with continuous cooling was added until the
solution was neutralized. (pH=7) This was done by check with litmus paper. After neutralization, (By portions)
5.006 g of sodium nitrite (NaNO2) followed by 5 mL of 6M HCl were added to solution. The solution in an ice bath
was then cooled for approximately an hour. The precipitated salmon pink crystals of [Co (NH3)5ONO]Cl2 was
then filtered. The crystals were then Washed with 20 mL of ice water then 20 mL of 95% ethanol. The crystals were
then Allowed to dry on the lab bench for approximately one hour before collecting the crystals for IR. The
measurement of this part was done by using graduated funnel to measure (ML) and weighting bowl of the grams in
the scale.

DISCUSSION
OBSERVATIONS AND CALCULATION
PART I: CHLOROPENTAAMMINECOBALT (III) C HLORIDE, [CO (NH3)5CL] CL2

[Co (H2O)6] Cl2 + 4NH4OH + NH4Cl + 1/2H2O2 → [Co (NH3)5Cl] Cl2 + 11H2O

Substance Amount Used

[Co (H2O)6] Cl2 9.993g
NH4OH 30.0 mL
NH4Cl 5.001g
30% solution H2O2 8.0 mL
Concentrated HCl 30.0 mL

Limiting Reagent:

The Cobalt compound [Co (H2O)6] Cl2 is the limiting reagent based on calculation and the thought

that only a set amount of reactant containing Co will be able to be converted into a set amount

of the final Co compound [Co (NH3)5Cl] Cl2.

Moles of [Co (NH3)5Cl] Cl2 = 9.993g /250.446 𝑔𝑚𝑜𝑙−1

= 0.040 mol

Theoretical mass of [Co (NH3)5NO2] Cl2 = 0.040 mol x RMM [Co (NH3)5NO2] Cl2

= 0.040 mol x 260.9975 g

= 10,519 g

% yield = 𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 /𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑑 x 100% = 6.098 g/ 10,414 𝑔 x 100% = 58 %

Observations for chloropentaamminecobalt (III) chloride, [Co (NH3)5Cl] Cl2

Due to the ligands in the compound color changes were observed during the experiment. During mixture of Co
solution, solution became orange. When the peroxide was added the color changed to a blackish red then redder
after gas evolved during stirring. When the solution was heated the color changed to a purple-red color.
Figure 1 UV-Vis Spectral data for 0.0025 M solution of [Co (NH3)5Cl] Cl2:
Figure 2 Infrared Spectral data for [Co (NH3)5ONO] Cl2

Concerning part 1 were included in the previous experiment where the compound was shown to be missing the
C=O bond (corresponding with structure) in the IR and the UV-Vis showed peaks at λ maxs analogous to the Co
ligand peaks and the observable color of the compound also corresponded to the spectral peaks.

Part II: Synthesis and characterization of [Co (NH3)5ONO] Cl2 and [Co (NH3)5NO2] Cl2

[Co (NH3)5Cl] Cl2 + NaNO2 → [Co (NH3)5ONO] Cl2 + NaCl

The Cobalt compound [Co (NH3)5Cl] Cl2 is the limiting reagent based on calculation and the thought that only a
set amount of reactant containing Co will be able to be converted into a set amount of the final Co compound [Co
(NH3)5NO2] Cl2.

The same calculation done for the experimental amount, except the usage 5.006 grams of

[Co (NH3)5Cl] Cl2.

1 mol of [Co (NH3)5Cl] Cl2 = 1 mol of [Co (NH3)5ONO] Cl2

2.396 x 10-3 mol of [Co (NH3)5Cl] Cl2 = 2.396 x 10-3 mol of [Co (NH3)5ONO] Cl2

Theoretical mass of [Co (NH3)5ONO] Cl2 = 2.396 x 10-3 mol x RMM [Co (NH3)5ONO] Cl2

= 2.396 x 10-3 mol x 260.9975 g

= 0.6254 g

% yield = 𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑/ 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑑 x 100% = 0.4644𝑔/ 0.6254𝑔 x 100% = 74.26%

Observations:

No Due to the ligands in the compound colour changes were observed during the experiment. When mixing and
heating the solution in the first steps the colour was red. After adding HCl and NaNO2 and cooling to form [Co
(NH3)5ONO]Cl2 the solution changed to a salmon pink colour. After drying and filtration the filtrate was an
orange tint and darkened after it isomerized over the drying period.

Figure 3 UV-Visible Spectral data for 0.0025 M solution of [Co (NH3)5NO2]Cl2:

Figure 4 Infrared Spectral data for [Co (NH3)5ONO] Cl2 :

CONCLUSION :

The data acquired from both parts of the experiment have shown the synthesis to have been completed of all
compounds. The IR spectrum showed a difference in peaks between 1000- 1500, around 1330 and the broad peak at
3240 was weaker in the final isomerized compound [Co (NH3)5NO2] Cl2. The NO2 peak in the ONO IR
spectrum missing helps to confirm functional groups within the final compound [Co (NH3)5NO2] Cl2. The UV-
Vis spectrum showed obvious difference in that in the isomerized compound one of the max peaks was not in the
visible spectrum at all but had moved to the UV region of the spectrum. The wavelengths show that the NO2
version of the compound was more difficult to excite e-. The slightly higher λ max of the ONO compound shows
that it is more easily excited. Though the similar wavelengths of both compounds show they contain the
same/similar contents i.e., the transition metal present in the compound is the same (Co). The colours absorbed
correspond with the observed colours of the compounds. [Co (NH3)5NO2] Cl2 had a slightly higher wavelength
and was observed to be darker in tint and more orange than red, and vice-versa for the [Co (NH3)5ONO] Cl2. This
supports the conclusion that there is a difference in the connectivity the ligands have when comparing the “before
and after” products, because this altered the λ max.