UNIVERSITY OF ZIMBABWE

NAME: MUTETE RONALD

REG NO: R164545P
PROGRAMM: CHH
COURSE: HCH102
EXPERIMENT NO.: 4
DATE: 10 OCTOBER 2107
TITLE: Transition metal complexes of cobalt(II)
AIMS:
 To prepare and compare complexes of cobalt, including nitro- and nitrito
isomers.
 To develop understanding of some different ways ligands can bond to metal
centres.

OBJECTIVES
1. To prepare [Co(NH3)5Cl]Cl2 using cobalt(II) chloride hexahydrate and
ammonium chloride
2. To prepare [Co(NH3)5NO2]Cl2, the nitro isomer
 MUTETE RONALD | R164545P

INTRODUCTION
Transition metal ions characteristically form coordination compounds, which are usually
coloured and often paramagnetic. A coordination compound typically consists of a complex ion,
a transition metal ion with its attached ligands and counter ions, cations or anions as needed to
produce a compound with no net charge. (Atkins, et al, 2010)
Another type of structural isomerism, is linkage isomerism, where the composition of the
complex ion is the same, but the point of attachment of at least one of the ligands differs. Two
ligands that can attach to metal ions in different ways are thiocyanate(SCN-) which can bond
through lone electron pairs on the nitrogen or the sulfur atom, and the nitrite ion(NO2-), which
can bond through lone electron pairs on the nitrogen or the oxygen atom. For example, the two
following compounds are linkage isomers:

 [Co(NH3)4(NO2)Cl]Cl2 – tetraaminechloronitrocobalt(II)chloride -yellow.

 [Co(NH3)4(ONO)Cl]Cl -tetraaminechloronitritocobalt(III)chloride – red.
(Zumdahl and Zumdahl,2003)
Linkage isomerism because some ligands (for example NO2- and SCN-) can coordinate to metals
to metals in more than one way. Isomeric nitrito and nitro complexes, for example contain -ONO
and -NO2 as ligands, and may be obtained by methods such as those indicated in the scheme:
dil
[Co(NH3)5Cl]Cl2 NH3 [Co(NH3)5H20]Cl3
NaNO2 NaNO2, conc. HCl
warm HCl
[Co(NH3)5ONO]Cl2 u.v [Co(NH3)5NO2]Cl2
red yellow
ligands which can coordinate in two different ways are sometimes known as ambidentate
ligands. (Sharpe, 2007)

Each ligand in a complex is a Lewis base, with at least one lone pair of the electrons that forms a
coordinate covalent bond to the central atom or ion. Because both of the electrons in the bond
comes from the ligand, we say that the ligand coordinates to the metal. Coordination compounds
are compounds with coordinate covalent bonds. They include electrically neutral complexes such
as Ni(CO)4 and ionic compounds in which at least one of the ions is a complex as in
K4[Fe(CN)6]. (Jones and Atkins, 2000)

Cobalt(II)compounds. This is the most stable oxidation state of cobalt in solution, and in the
absence of strong complexing agents such as NH3 and CN-, for example Co2+ complexes
containing NH3 and CN- ligands are readily oxidized to Co3+ complexes. (Liptrot, 1983)

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Some ligands may attach to the central metal ion of the complex ion in different ways. For
example, a nitrite ion, a monodentate ligand, has electron pairs available for coordination both on
the N and O atoms.

Whether attachment of this ligand is through N or O tom,

the formula of the complex is unaffected. The properties of
the complex ion, however may be affected. When the
attachment occurs through the N atom, the ligand can be
referred to as nitro, and coordination through an O atom
nitrito.

(a) [Co(NO2)(NH3)5]2+ (b) [Co(ONO)(NH3)5]2+

(Petrucci, et al, 2002)

PROCEDURE
Part1: Preparation of [co(NH3)5Cl]Cl2
The procedures were carried out in the fume cupboard working in pairs. A mass of 5.0g of
ammonium chloride was dissolved in concentrated 0.88 ammonia(30cm3) in a 250cm3 conical
flask. The solution was continually agitated whilst adding cobalt(ii) chloride
hexahydrate(CoCl2.6H2O) (10.0g) in 2-3g portions, making sure that each portion reacted before
the next portion was added. Initially a precipitate of [Co(NH3)6]Cl2 was formed with the
evolution of heat. To the warm slurry/solution, 30% hydrogen peroxide (8cm3) was added with
care in small portions (with efficient stirring). This resulted in a vigorous exothermic reaction
with effervescence. A deep red solution of [Co(NH3)5(OH2)]3+ was formed. After cooling in an
ice bath, 30cm3 of concentrated hydrochloric acid was slowly added. The reaction mixture was
gently heated with stirring until a purple product precipitated, (typically after 20-30minutes)
from a blue-green supernatant liquid. Heating of the solution was done with care, not allowing
the solution to boil. The reaction was complete when the supernatant liquid was deep blue in
colour. The mixture was then cooled to ambient temperature and filtered to obtain the solid
product, on a Buchner filter. Washing with several portions of ice cold water followed, and then
with a small quantity of acetone before drying in the air. The product was a dry powder. The
mass of the product was obtained and recorded.

Transition Metal Complexes of Cobalt (II) Complexes 3

 MUTETE RONALD | R164545P

Part 2: preparation of [Co(NH3)5NO2]Cl2, the nitro-isomer

Working in a fume hood, 1.0g of [Co(NH3)5Cl]Cl2 was dissolved in a mixture of concentrated
(0.88) ammonia solution (2.4cm3) and water (20cm3) by heating at the boiling point. The hot
solution was rapidly filtered through a Buchner funnel, the filtrate was cooled in an ice bath and
acidified slightly to about pH 6 by the addition of dilute hydrochloric acid, and checking with
indicator paper using glass rod and white tile. 1.2g of sodium nitrite was added to the cold
solution. The resultant mixture was heated until the red precipitate that initially formed had
completely dissolved. Heating was continued until the solution was dark yellow-brown in colour.
The dark yellow solution was cooled and then 6cm3 of concentrated hydrochloric acid was
added. The brown yellow crystals were collected by filtration. The product was washed with a
small quantity of acetone, followed by drying in the air. The mass of the product was determined
and the percentage yield (based on the amount of [Co(NH3)5Cl]Cl2 used). the product was placed
in an appropriately labelled sample bag and handed in to the demonstrator for marking.

RESULTS AND CALCULATIONS

Table 1: weighing of ammonium chloride

Mass of empty container + sample/g 9.35

Mass of empty container/g 4.27
Mass of ammonium chloride/g 5.08

Table 2: weighing of the product, [Co(NH3)5Cl]Cl2

Mass of empty container + sample/g 6.22

Mass of empty container/g 0.36
Mass of sample obtained/g 5.86

Table 3: Weighing of [Co(NH3)5Cl]Cl2 for part 2

Mass of empty container + sample/g 5.31

Mass of empty container/g 4.27
Mass of sample/g 1.04

Table 4: weighing of the product [Co(NH3)5NO2]Cl2, the nitro isomer

Mass of empty container + sample/g 0.92
Mass of empty container/g 0.34
Mass of sample/g 0.58

Transition Metal Complexes of Cobalt (II) Complexes 4

 MUTETE RONALD | R164545P

Percentage yield (based on the amount of [Co(NH3)5Cl]Cl2 used)

Percentage yield=
(number of moles of product) ÷ (number of moles of [Co(NH3)5Cl]Cl2 used) × 100%
Moles of [Co(NH3)5Cl]Cl2 used = mass/Mr
= 1.04/264.446
=0.004153mol
Moles of [Co(NH3)5NO2]Cl2 produced = mass/Mr
= 0.58/264.445
=0.002193mols
Thus, percentage yield = (0.002193 ÷ 0.004153) × 100%
= 52.81%
Equation for the formation of the product:
[Co(NH3)5Cl]Cl2(s) + NaNO2(s) + H2O = [Co(NH3)5(NO2)]Cl2(s) + NaOH(aq) + HCl

DISCUSSION
The first part of the experiment was done successfully and obtained a high yield of 5.86g
[Co(NH3)5Cl]Cl2, exceeding the required minimum weight of 5.5g. the product had the colour
purple, which concurs with the theoretical colour of [Co(NH3)5Cl]Cl2 complex. This is proof that
the experiment was correctly and accurately carried out on this part with little or no challenges to
discuss. This part of the practical however needed very careful and alertness on the stage of
heating the reaction mixtures, but not allowing to boil. Avoiding to boil the reactants whilst
heating directly from a Bunsen burner flame was risky (high chances of boiling) as compared to
the alternative of heating the reactants from a hot water bath (placed on a Bunsen burner).
The second part of the experiment was carried successfully, but the obtained product simple did
not meet the required expectations. Only a small mass of 0.58g of the sample was produced, the
colour of the product sample did not tally with the theoretical colour of [Co(NH3)5NO2]Cl2,
yellow. The sample was brownish-red instead, indicating that, some procedures in the practical
were not correctly executed. At stage 1, filtration might not have been effective since the
solution was immediately poured into the Buchner funnel whilst, the filter paper was dry and not
adhering to the base of the funnel. Notable error was that, the filtrate was supposed to be slightly
acidified to pH about 6. However, HCl was mistakenly added to excess amounts, such that the
pH could have been pushed well below 6. Under very low pH, the reaction of the solution with
NaNO2 might have been hindered in a way such that, the purple [Co(NH3)5Cl]Cl2, a start reagent,
might still had been present in the end product, thus imparting the reddish colour. Another

Transition Metal Complexes of Cobalt (II) Complexes 5

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explanation could be that, instead of producing the nitro- isomer, the [Co(NH3)5ONO]Cl2 nitrito-
isomer (which is red) could have been produced along with the nitro- compound. The very low
pH might have influenced some oxidation tendency, thus favouring the formation of the nitito-
isomer as in the reaction equation below:
HCl / O
[Co(NH3)5Cl]Cl2 NaNO2 2 [Co(NH3)5(ONO)]Cl2 (red)
The NO2- ligand would then have attached to the Cobalt center using the O2 atom.

CONCLUSION
Percentage yield for the product [Co(NH3)5NO2]Cl2, the nitro isomer is 52.81%

REFERENCES
1. Atkins P, Overton J, Rourke P, Weller M, Armstrong F, 2010, Inorganic Chemistry, 5th
edition, Oxford University Press, Great Britain, page 232

2. Zumdahl S.S and Zumdahl A. S, 2003, Chemistry, 6th edition, Houghton Mifflin Company,
Boston, New York, page 1004

3. Sharpe G. Allan, 2007, Inorganic Chemistry, 3rd edition, Pearson Education Ltd, and Dorling
Kindersley Publishing Inc, New Delhi, India, page 454

4. Jones L and Atkins P, 2000, Chemistry- Molecules, Matter, and Change, 4th edition, W.H
Freeman and Company, New York, page 935

5. Liptrot F. G, 1983, Modern Inorganic Chemistry, 4th edition, English Language Book
Society, Great Britain, page 383

6. Pretrucci H. R, Harwood S. W, Herring F. G, 2002, General Chemistry, Principle and

Modern Application, 8th edition, Prentice Hall, Upper Saddle River, New Jersey, page 993

Transition Metal Complexes of Cobalt (II) Complexes 6