Gory 1.
Olson Synthesis and Reactions of Cobalt Complexes
Stanford University
Stanford, California 94305
A laboratory experiment
A laboratory course in introductory col-
lege chemistry should provide experiments which give
some insight into the spirit of chemical investigation as
well as illustrate useful laboratory techniques and basic
chemical principles. The experiment described here is
intended to fulfill these requirements by the study of a
series of reactions employed in the synthesis of a num-
ber of coordination compounds of cobalt(I1) and cobalt-
(111). The cobalt complexes were chosen for this study
because each ligand substitution alters the electronic
distribution about the cobalt ion and thus creates
significant color changes in the products.
I n the first of two three-hour laboratory periods,
students prepare carbonatopentaammine cobalt (111)
nitrate, I, the precursor for subsequent reactions.
A solution of cobaltous nitrate and ammonium car-
bonate in aqueous ammonia is oxidized by passing
oxygen gas through the solution over a period of 1.5-2
hr.' Since the reaction product, I, has an absorption
maximum at 510 mr, the progress of the reaction may
be monitored spectrophot~metrically~~~ using an aliquot
of the reaction mixture diluted with concentrated am-
monia (dilution with water causes precipitation of
cobalt(I1) hydroxides).
I n an attempt to understand something about the
deeply colored complex which is formed in the solu-
tion prior to oxidation, a series of test tube color com-
parison reactions are performed. The products com-
pared are produced by adding a source of carbonate ion
and ammonia separately, and then in the reverse order
to a small amount of cobaltous nitrate solution. When
these tests are done carefully, students can observe the
formation of [ C O ( N H ~ ) ~ ][Co(NH&I3+
~+, (by aerial
oxidation in the test tube), cobalt(I1) hydroxide, and
cobaIt(I1) carbonate. The students were asked to
propose structures for these compounds. The im-
portant point which they must recognize in their pro-
posals is that they have evidence, and not proof for the
existence of certain complexes. By considering pos-
sible alternatives, however, the most likely structure
can be assigned. I n one reaction for example, a single
drop of ammonia is added to the cobaltous nitrate solu-
tion, and a solid immediately precipitates. Upon add-
ing more ammonia, the solid dissolves to give an amber
solution. The most reasonable explanation for these
observations is that the solid which precipitates is
508 / Journal o f Chemical Education
cobalt(I1) hydroxide, formed because of the change in
pH of the solution. Further addition of ammonia then
produces a souble ammonia-cobalt(I1) complex which
may be hexaammine, aquopentaamine, diaquotetra-
ammine, etc. Given the information4 that 11, the
peroxobridged species
NHs
H3N I NH, HaN, I ,NHa
HaN' 1 \ 0 4 " I\m.
NHs NHa
I1
is an intermediate in the oxidation of cobalt(I1) to
cobalt(II1) in ammonia solution, the most likely com-
plexes which can be suggested are the hexaammine and
the aquopentaammine. Since cobalt(I1) complexes
are unusually labile," the solution probably contains an
equilibrium mixture of the various species.
On the basis of all of their observations, students
were then asked to suggest a structure for the dark-
colored complex they were oxidizing on large scale, and
to write a pathway for its formation and its conversion
to product. The students were given the additional
information that the decomposition of the peroxo-
bridged compound, 11,to products is accelerated by the
addition of chloride ion or carbonate (Evidently
these ligands increase the rate of 0-0 bond cleavage or
assist in displacing hydroxide ion or water after 0-0
bond scission.) The success with which some students
assembled the information irito reasonable proposals
showed that they were capable of handling the problem
with a minimum of theoretical introduction and a
significant amount of deductive reasoning. Several
students even suggested isotopic labelling experiments
which would demonstrate if any oxygen in the car-
bonate ligand of I could have come from the oxygen
used in the oxidation.
I n the second week of the experiment, the complex I
is treated as diagrammed in Figure 1.
Complex I is pink, and the formation of the darker
iodide, 111,with excess potassium iodide1 illustrates the
law of mass action (use of excess I- to force the equi-
librium in the desired direction) and the ideas of solu-
'The proeedme used here was adapted from that given by
WERNER and GOSLINGS, Bel.., 36, 2380 (1903), and Inorganic
Syntheses, 4, p. 171.
A Bausch and Lamb Spectronic 20 was used for this purpose.
* Following the rate of appearance of the product is an inters6
ing extension of the experiment, although unnecessary since the
oxidation is complete in less than 2 hr.
Bnsom, F., AND JOHNSON, R . C., "Coordination Chemis-
try," W. A. Benjamin h e . , New York, 1964, pp. 01-92, and
SCHAEFER, W., Imrg. Chem., 7, 725 (1SGR).

IJI
Figure 1. Reactions of the [Co(NHalsC031+complex.
bility behavior (smaller anions form more soluble salts
with the same cation).
The reaction of I with acid' liberates COz with the
overall substitution of HzO to form the aquopenta-
ammine IV. When the same reaction is carried out in
the presence of nitrite ion, the two complexes VI and
VII are formed. These reactions show that under the
conditions of the experiment? the strength with which
the ligands are bound decreases in the order NO2-,
HiO, NO%-. An interesting point is that although the
NHa ligand to cobalt(II1) is not replaced in the scheme,
it is known from spectral evidence6 to be more weakly
bound than NO,-. The observed stability is due to the
difficulty of removing the second ligand- to form the
tetraammine.
I n the formation of the complexes VI and VII, two
advanced ~ r i n c i ~ l ecan
s be illustrated. Careful ob-
servation of the reaction mixture after the evolution of
COZshows that it contains a pale pink solid which be-
comes yellow upon standing about 10 min a t room tem-
perature. This color change is due to the isomeriza-
tion of the initially formed, oxygen bound ligand of the
NOz- group to the nitrogen bound ligand.' Thus the
definition of isomers and isomerization can be intro-
duced here, and a fairly detailed discussion of kinetic
and thermodynamic control of reaction pathways may
be presented.
I n the last reaction, the aquopentaammine IV is
heated in vacw to remove water. The vacant co-
ordination site is then occupied by a nitrate ion from
the crystal lattice to form the nitratopentaammine, V.
Experimental
Carbonatopentaammine cobalt(ll1) nitrate, I. Ammonium ear-
bonate powder (150 g) and hot water (150 d ) are mixed in rt 1-1
erlenmeyer flask, 250 ml of concentrated aqueous ammonia is
added, and the mixture swirled until dissolved. To the solution
is added 100 g of cobaltous nitrate (Co(NOa)r6H.0) dissolved in
50 ml of hot water. Oxygen gass is bubbled through the solution
using a gas dispersion tuhe a t s. moderate rate which permits
both saturation of the solution with oxygen and mild agitation.
If the reactiau cannot he carried out in a hood, ammonia vapon
may he carried away by means of a tuhe connected to a water
aspirator.* After 1.5-2 hr, the solution is transferred to an 800
ml beaker and placed in a refrigerator (near 0°C) until the follow-
ing laboratory period. The crystalline product is then collected
on a Biichner funnel, washed with 2.5 ml of ice water, 50 ml of
acetone, pressed dry with a. rubber dam," and partially dried in
air. Abotlt 45 g of dark red crystds are obtained.
Carbonalopntaammine cobalt(II1) iodide, 111. Five grams of
earhonatopentsammine eohalt(II1) nitrate, I , is dissolved in 20
ml of water with heating to 8C-9O0C. Powdered potassium
iodide (6.3 g) is ndded and the mixture stirred until all of the
salid is dissolved. The iodide salt, 111, crystallizes from the
solution upon coalingin ice for a. few minutes. The reddish brown
produet is collected using a Bixhner funnel, washed with 20 d
of acetone. and air dried.
COBALTOUS NITRATE (NHdzCO, * NH3
: A
(SOLUTIONS I) (SOLUTION 2)
l drop
5 ml
NH3
E K2C03
(SOLUTION 3 )
- F
Figure 2. Cobdtour nitrate test reactions,
Aquopenlaammine cobolt(I1I) nitrate, IV. Five grams of car-
honatopentaamine cohalt(II1) nitrate, I, is stirred in 12 ml of
water darine the addition of 10 ml of 6 N nitric acid. When the
COS evolution is complete (10 min) the mixture is diluted with
50 ml of methanol and the light-pink product, IV, collected,
washed with acetone, and air dried.
Nilrito- and nitropataammine cobalt(ll1) ni(mles, VI and VII.
Five grams of earbonatopentaamine cohalt(II1) nitrate, I, and
5 g of sodium nitrite are mixed with 12 ml of water and 5 ml of
6 N nitric acid is added slowly and cautiously with stirring. The
reaction should be done in a. hood or with an aspirator to remove
the NOp fumes. As soon as the CO. evolution has stopped, the
suspended salid is the pink, oxygen bound nitrito complex VI
which isomeriaes to the stable, nitrogen-hound nitro complex VII
when allowed to stand for 10-16 min a t room temperatme. The
suspension is diluted with 100 ml of methanol and the yellow
solid VII collected as before.
Nilratopenlaammine coball(lI1) nilrate, V. About 0.5 g of
aquopentaammine eobalt(II1) nitrate, IV, is placed in a heavy-
walled test tuhe connected to aspirator vacuum through a trap.
The tube is heated under good vacuum in a beaker of boiling
water with occasional shaking over a period of 20 min, or until
constant weight is achieved. The color of the complex gradually
changes to a deep red as the salid V is formed and water is lost.
Cobalt(I1) nitrate test readions (Fig. &). One gram of cobaltous
nitrate is dissolved in 10 ml of water and the solution divided
into equal portions in three test tubes (solutions I). Ammonium
carbonate (0.5 g) is dissolved in 5 ml of water and 5 ml of am-
monia (solution 11), and 0.5 g of potassium carbonate is dissolved
in 10 ml of water (solution 111). The reagents are combined as
indicated in Figure 2. A is a solotion having the light magenta
color of the preparative reaction mixture before oxidation; B is
the pale lavender solid, cobalt (11) carbonate; C is tho same as
A; D is eobalt(I1) hydroxide, a blue precipitate which dissolvm
in excess ammonia to form E, the labile eobalt(I1) ammine eom-
plex. E undergoes a slight color change upon adding carbonate
and producing F, which has the same appearance as C and A.
Conclusion
One of the goals of modern chemistry is the elucida-
tion of the pathway of chemical reactions and the de-
Since water is the solvent for these reactions, the fact that
the aquopentaammine IV is formed in preference to the nitrato-
pentaammine V may reflect the effect of the 55 Af caneentrrttion
of water. Spectral studies (see footnote 6) have shown that the
aqua ligand is more strongly bound to cobalt(II1) than the
nitrato ligand.
' COTTON,F. A,, A N D WILEKINSON, G., "Advanced Inorganic
Chemistry," Interscience Publishers (division of John Wiley &
Sons Inc.). New York. 1962. D. 579.
iba.,
B A ~ O L OAND JOHNSON, p. 78.
8 Although air may be used for the oxidation (see footnote 1)
the reaction time is substantially increased to 10-12 hr. We
found that 100 such oxidatiuns required five 200 it3 cylinders of
oxygen.
' T h e only time that an aspirator is inadequate is when the
ammonia is measured and transferred to the large flask.
lo FIESER, L., AND FIESER,M., "Reagenb for Organic Syn-
thesis," John Wiley &Sons, Inc., New York, 1967, p. 488.
Volume 46, Number 8, August 1969 / 509
velopment of qualitative relationships upon which the
behavior of molecules mav be nredicted. A freshman
chemistry laboratory course can provide the inspiration
to pursue the field of chemical investigation only if
aspects of current research problems and methods of
scientific reasoning are demonstrated in its experi-
ments and by its instruction. The experiment de-
scribed in this paper can fulfill these requirements by
introducing first-year chemistry students to some of
510 / Journal of Chemical Education
the thought processes, technique, and spirit of modern
-
chemicalinvesti~ation.
Acknowledgmenl
I would like to thank Drs. R. H. Eastman, P. F.
Linde, and C. Hamilton for permission to include this
experiment in the Stanford University general chem-
istry laboratory curriculum and for their helpful com-
ments.