EXPERIMENT 2

PREPARATION OF SOME COBALTAMMINE COMPLEXES

AIM:
To synthesise and study the cobaltammine complexes
To study the UV characterization of the cobaltammine complexes

Abstract:
This experiment serves as an introduction to the area of synthetic chemistry and more
specifically, to inorganic synthesis. New chemical bonds will be formed large molecule
is synthesized from smaller ones. Coordination compound will be synthesised. The
bonds in coordination compounds are two-electron bonds (like covalent bonds), but
both electrons come from the ligand (a Lewis base with an unpaired electron pair). The
metal ion serves as a Lewis acid (an electron-deficient species which can use its empty
orbitals for the bond). Two possible coordination complexes will be synthesized in this
experiment. One molecule is named carbonatotetraamminecobalt(III)nitrate. Its formula
is written [Co(NH3)4Co3]NO3. The other molecule is named
pentaamminechlorocobalt(III) chloride. Its formula is written [Co(NH3)5Cl]Cl2. The
ammonia and chloride ligands of these complexes use lone pairs of electrons to form
bonds with the cobalt cation. The coordination number for the cobalt in both products is
six and these cations are octahedral, as predicted by VSEPR theory.

INTRODUCTION:

Cobaltammine complexes (Co(NH3)4Co3)NO3 and (Co(NH3)5Cl)Cl2 have played a

considerable part in the development of coordination chemistry. Werner, for example,
developed his ideas of coordination number and geometry through studying complexes
of Co(III) and Pt(IV) with amines Cl, Br, I, pyridine, CN, etc. Werner coordination
complexes are compounds formed between transition metal ions and a variety of
organic and inorganic ions or neutral molecules(Saunders, 1997).

The elucidation of the details of the structure of these complexes is of current interest,
although Werner correctly predicted the geometry of many of them more than fifty years
ago. A well-known complex ion is the tetraammine copper(II) ion in which four ammonia
molecules are arranged (coordinated) about a central cupric ion at the corners of a
square. The nature of the bonds between the central atom and the coordinating groups
(termed ligands) varies with the nature of the species involved. In some complexes the
bonding may be described as largely covalent in character, whereas in others electron
sharing is relatively unimportant and the interaction between the central atom and the
ligands is essentially electrostatic in nature(Walton, 1948).
Coordination compounds of Co(III) and Cr(III) have been of particular interest because
their complexes undergo ligand exchange very slowly compared with complexes of many
other transition metal ions. For example, Ni(NH3)62+ reacts virtually instantaneously with
H2O to form Ni(OH2)62+. Under the same conditions, the analogous reactions of
Co(NH3)63+ and Cr(NH3)63+ occur very slowly. This difference in behaviour of complexes
of different metal ions has been qualitatively accounted for by ligand field theory and
molecular orbital theory(Dixon et al, 1983).

The slow reactivity of Co(III) complexes has made them suitable for extensive
investigations. The structures of the octahedral Co(III) complexes which will be prepared
in this experiment are given below.

The synthesis of [Co(NH3)4CO3]NO3 is carried out according to the unbalanced equation:

Co(NO3)2 + NH3(aq) + (NH4)2CO3 + H2O2 [Co(NH3)4CO3]NO3 + H2O + NH4NO3

The Co(NO3)2 that is available commercially has the formula Co(NO3)26H2O and very
probably is a coordination compound having the ionic formulation [Co(OH2)6](NO3)]2.
Since Co(II) complexes, like those of Ni(II), react very rapidly by ligand exchange, the first
step in the reaction might be expected to be:

[Co(OH2)6]2+ + 3NH3 + CO32 [Co(NH3)4CO3] + 6H2O

This Co(II) complex could then be oxidised by the transfer of an electron to H 2O2 to give
the relatively unreactive Co(III) ion, [Co(NH3)4CO3]+.

The preparation of [Co(NH3)5Cl]2+ is accomplished from the carbonato complex according

to the following series of equations:

[Co(NH3)4CO3]+ + 2HCl [Co(NH3)4(OH2)Cl]2+ + CO2(g) + Cl

[Co(NH3)4(OH2)Cl]2+ + NH3(aq) [Co(NH3)5(OH2)]3+ + Cl

[Co(NH3)5(OH2)]3+ + 3HCl [Co(NH3)5Cl]Cl2(s) + H2O + 3H+

The two complexes are characterised by infrared and U/V-visible spectroscopy and by
electrical conductivity measurements(Richens et al, 2003).

MATERIALS:
 Beaker
Spatula
Magnetic stirrer
Fume hood
Filtration flask
Suction apparatus
Pinch clamp
Thermometer
Evaporating dish
Oven
Spectrophotometer
Vacuum filtrations
Volumetric flasks
Analytical balance
Pipet

REAGENTS AND SOLUTIONS:

A solution of (NH4)2CO3 +H2O+Concentrated aqueous ammonia.

A solution containing 15g (0.05 mole) of [Co(OH2)6](NO3)2 in 30ml of distilled
water.
30% H2O2 solution
[Co(NH3)4CO3](NO3)
Concentrated HCl
Ethanol
Distilled Water

EXPERIMENTAL PROCEDURE:

Synthesis of Carbonatotetraamminecobalt(III)nitrate

20 g (0.21 mole) of (NH4)2CO3 was dissolved in 60 mL of H2O and added 60 mL of

concentrated aqueous NH3. While stirring, this solution was poured into a solution
containing 15 g (0.05 mole) of [Co(OH2)6](NO3)2 in 30 mL of H2O. Then slowly added 8
mL of a 30 per cent H2O2 solution. (Handle H2O2 with rubber gloves. If the affected area
is not washed immediately with water, hydrogen peroxide can cause severe skin burns.)
The solution was poured into an evaporating dish and concentrate over a gas burner in a
hood not allowing it solution to boil. During the evaporation time add, 5 g (0.05 mole) of
(NH4)2CO3 was added in small portions. Suction filtered (with water aspirator; for better
control of the vacuum, used a pinch clamp on the rubber tubing between the trap and
filtration flask; see Figure I.1) the hot solution and cooled the filtrate in an ice water bath.
Under suction, the crystals of the red product were filtered off.The [Co(NH3)4CO3]NO3 in
the filtration apparatus was washed first with a millilitre of water (the compound is
somewhat soluble) and then with a similar amount of ethanol. Dried in the oven and
Calculated the yield.

Synthesis of Pentaamminechlorocobalt(III)chloride

5.0 g of [Co(NH3)4CO3]NO3 was dissolved in 50 mL of H2O and added concentrated HCl

(5 to 10 mL) until all the CO2 is expelled. Neutralised with concentrated aqueous NH3
and then added about 5 mL excess. The solution was Heated for 20minutes, again
avoiding boiling; [Co(NH3)5(OH2)]3+ was formed. Tthe solution was cooled slightly and
added 75 mL of concentrated HCl. Reheated for 20 to 30 minutes and observed the
change in colour. Purple-red crystals of the product separate on cooling to room
temperature. The compound was washed several times, by decantation, with small
amounts of ice-cold distilled water, then filtered under a water aspirator vacuum with glass
fritted funnel (medium porosity). Washed with one millilitre of ethanol,dried in an oven,
and Calculated the yield.

PRESENTATION OF RESULTS:

A)
Name of the product: Carbonatotetraamminecobalt(III)nitrate
Mass of the product: 4.14g
Color of the product: Purple

Table 1: Absorbtion spectra Of Carbonatotetraamminecobalt(III)nitrate

 Wavelenth Absorbance
(nm) (ABS)
350 2.099
400 2.113
450 1.548
500 1.541
550 1.196
600 0.178
650 0.515
700 0.463
750 0.378

B)

Name of the product: Pentaamminechlorocobalt(III)chloride

Mass of the product: 0.82g

Color of the product: Purple

Table 2: Absorption spectra of Pentaamminechlorocobalt(III)chloride

Wavelenth Absorbance
(nm) ABS
350 1.381
400 2.110
450 1.612
500 1.451
550 1.180
600 0.940
650 0.746
700 0.100
750 0.087

DISCUSSION OF RESULTS:
The experiment was taken done in one day and it was done in a fume hood.

Ammonium carbonate, used as a smelling salt, is an irritant to the mucous membranes

and reactions was kept in a fume hood as much as possible. Before weighing, the bottle
was opened in the hood to remove ammonia vapor from the bottle. Cobalt nitrate
hexahydrate is hygroscopic and absorbs atmospheric moisture. Thus a top loading
balance was used for the synthesis and an analytical balance in the characterization
step. A solution of 20g (0.21 mole) of (NH4)2CO3 + 60 ml of distilled water + 60ml
concentrated aqueous NH3 into the solution of containing 15 g(0.05 mole) of
[Co(OH2)6](NO3)2 in 30 ml of distilled water, and 8 ml of 30% hydrogen peroxide was
poured in an evaporating dish and concentrated over a gas burner in a hood 90-100
ml.Evaporating dish was used in place of beaker to facilitate evaporation and the
solution was maintained near a temperature of 85% and not allowing it to boil because
boiling can result in loss of some of the reagents.to the solution 5g (0.05 mole) of
(NH4)2CO3 was added to the solution to form precipitates and then suction filtered the
hot solution,cooled in 5 degrees Celsius of ice bath then isolated the red crystalline
product by suction filtration into a clean side-arm Erlenmeyer flask. The filtrate was
transferred into a separate 250 mL Erlenmeyer flask and retain. the product was
washed with a small amount of ice-cold water and then with a small amount of 95%
ethanol to remove the impurities.Then it was dried and weighed and got the mass of
4.14 which was below the expected mass which range between 5-6,this was due to
experimental errors.The absorption spectra of carbonatotetraamminecobalt(III)nitrate
was observed to have a maximum absorbance at the wavelength of 400 nm and
minimum absorbance at the wavelength of 600 nm.

Part b.) On the synthesis of Pentaamminechlorocobalt(III)chloride,5.0g of

[Co(NH3)4CO3]NO3 was supposed to be used but because of smaller mass produced in
part A,every number on the procedure was multiplied by a factor of 0.828(5.0g/4.14g)
and the mass of 4.14g was used thus changing the time and amounts of the reagents in
the procedure. The solutions used for washing were cold to prevent the loss of product
by redissolving. Removal of remaining solvent was accomplished by drying in an oven
at 100-120C to yield [Co(NH3)5Cl]Cl2 and the mass was 0.82g which was within the
expected range.The absorption spectra was observed to have maximum absorbance at
the wavelength of 400 nm and minimum absorbance at the wavelength of 750 nm.
Conclusion:

The experiment was successful and the aim of the experiment (to synthesize some
cobaltammine complexes and to study their absorption spectra) was achieved and the
two cobaltaammine complexes synthesized are carbonatotetraamminecobalt(III)nitrate
and Pentaamminechlorocobalt(III)chloride and they were found to have 4.14 g and 0.82
g mass.

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