16 Cobalt

16.1 The Element

Cobalt compounds have been used in coloured glass for at least 4000 years but the
metal has been produced industrially only during this century. It is a widely
distributed but relatively uncommon element in the earth's crust. It occurs
biologically in vitamin B12 , which contains Co 3+ bonded octahedrally to five nitrogen
atoms (four from pyrroline rings and one from a benzimidazole ring) and the carbon
atom of a eN- group. The industrial extraction of the metal is usually an ancillary
process to the extraction of other metals such as copper and lead.
Cobalt (4s2 3d7 ) stands between iron and nickel in group VIII and above rhodium
and iridium. It shows high oxidation states even less willingly than iron, +3 being the
highest oxidatio:-- state of any significance. Cobalt resembles iron and nickel in
appearance, and like these metals it is ferromagnetic; it finds uses in a variety of steels
designed to have specific magnetic properties. The massive metal is oxidised in air
above 300° with the formation of Co 3 0 4 and CoO. Steam forms CoO at red heat.
Many nonmetals react when heated with cobalt; fluorine gives CoF 3 , the other
halogens giving CoX 2 . Cobalt is more resistant than iron to attack by mineral acids,
and it is not attacked by dilute alkalis.

16.2 Compounds of Cobalt(III) (d 6 )

The important oxidation states of cobalt in aqueous solution are +3 and +2. The
nature of the ligand bonded to cobalt has a dramatic effect on the stabilities of
these oxidation states. Simple compounds of cobalt(III) are strong oxidising agents,
and in water the [Co(H 2 0) 6 ] 3 + ion is a very powerful oxidising agent; it oxidises
water to oxygen
[Co(H20) 6 ]3+ + e -+ [Co(H20)6 j2+ (E' = +1.84 V)
However, other ligands, for example ammonia, stabilise the cobalt(III) state to varying
extents in aqueous solution
[Co(NH 3 ) 6 ]3+ + e -+ [Co(NH 3 ) 6 j2+ (E' = +0.11 V)
With some ligands, for example eN-, the stabilisation of the +3 state is so great that
the cobalt(II) complex reduces water to hydrogen
[Co(CN)6 j3- + e -+ [Co(CN) 5 j3- + CW (F = -0.8 V)
Further, the cobalt(II)-cyanide complex will even react with hydrogen to produce
what is regarded as a cobalt(III) complex
2[Co(CN) 5 ]3- + H2 -+ 2[Co(CN) 5 Hj3-
There is thus no simple aqueous chemistry of cobalt(III) but there is an
extensive range of complexes. For cobalt(II) the reverse is true; simple salts and
aqua-complexes are stable in aqueous solution but the addition of other ligands
makes for more facile conversion into the +3 state.
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D. Nicholls, Complexes and First-Row Transition Elements
© D. Nicholls 1974
186 COMPLEXES AND FIRST-ROW TRANSITION ELEMENTS
16.2.1 Simple Compounds
Cobalt(III) fluoride. CoF 3 is a light-brown powder which reacts violently with
water with evolution of oxygen. It is obtained by the action of fluorine on the
heated cobalt(II) halides CoF 2 or CoC12 • It is a useful fluorinating agent; for
example, it converts hydrocarbons into fluorocarbons
4CoF 3 + -CH 2 - -+ -CF2 - + 4CoF 2 + 2HF
With N2 0 5 the green crystalline nitrate Co(N0 3 h is formed.
A blue hydrate CoF 3 .3.5H2 0 has been prepared by electrolytic oxidation of
CoF 2 in 40 per cent HF. It oxidises water like the simple fluoride.
The other cobalt(III) halides are unknown, cobalt(m) being too strong an
oxidising agent to exist solely with chloride, bromide, or iodide ions.
Cobalt(III) oxide. The oxidation of Co(OH) 2 in alkaline media gives a brown
precipitate of uncertain structure; it is best written as Co 2 0 3 .aq. When this is
dried at 150° the composition Co 2 0 3 .H2 0 is formed, which is probably CoO(OH).
On further heating to 300°, oxygen begins to be evolved (as well as water) and
black Co3 0 4 is formed. The dark-brown CoO(OH) is formed when Co(OH) 2 is
heated in air at 100°; it has a layer lattice in which each cobalt is surrounded
octahedrally by oxygen atoms.
Cobalt(m) sulphate. This is the most readily available cobalt(III) salt. The
hydrate Co2 (S0 4 h .18H2 0 is prepared by oxidation of cobalt(II) sulphate in
8N H2 S0 4 either electrolytically or with ozone or fluorine. It is stable in the dry
state but liberates oxygen from water. Some alums, for example KCo(S0 4 ) 2 .12H2 0,
can be crystallised from sulphuric acid solutions; they, like the hydrated sulphate,
are believed to contain the [Co(H 2 0) 6 ] 3 + ion. As well as being acidic (hydrolysis
to [Co(OH) (H 2 0) 5 ] 2 + occurs in O.IM perchloric acid), this ion is a strong
oxidising agent. Therefore no salts of organic anions such as formate, tar-
trate, and citrate can be obtained since these anions are oxidised to carbon
dioxide and water by [Co(H 2 0)6 p+. However, cobalt(m) acetate is believed to be
present in dilute acetic acid solutions of cobalt(II) acetate that have been oxidised
with ozone.

16.2.~ Complex Compounds

We discussed in chapter 1 the part played by cobalt(III) complexes in the historical
development of co-ordination chemistry. The fact that cobalt (III) forms an enor-
mous number of octahedral compiexes having the inert t 2 g6 configuration has
resulted in these being used extensively for rate and mechanistic studies on octa-
hedral substitution reactions (chapter 8).
Cobalt(III) has a great affinity for nitrogen donors especially ammonia, amines,
nitro -N0 2 , and -NCS groups. Other ligands such as water molecules, halide,
hydroxide, or carbonate ions may also be present in these complexes with
nitrogen donors, and various stereoisomers can often be isolated from such mixed
ligand systems. The preparation of these complexes usually involves the addition
of the nitrogen donor to a cobalt(ll) solution followed by oxidation with air or
hydrogen peroxide. Perhaps the most famous of these compounds are the
cobaltammines. The orange hexammines, containing the [Co(NH3 ) 6 ] 3+ ion, are
obtained from solutions of cobalt(II) salts in aqueous ammonia in the presence of