Coordination Complexes 231

(b) Five grams of the acid-free irans-dichloro chloride

(No. 131) are dissolved in 50ml of water and 2.5g of anhy
drous sodium sulfite are added. The green solution which
turns brownish-yellow, is stirred until the sulfite has dis
solved. While this is cooling in ice one hundred milliliters
of 95% alcohol are added slowly and the solid that precip
itates is filtered off and drained well. The yellow product is
recrystallized by dissolving it in 15ml of hot water, cooling
it in ice, and adding 15ml of methanol. The purified material
is washed on the filter with methanol and ether.
Yield = 4.5g
Reference: Werner, Ann., 386:81 (1912).

127 d. Sulfatobis(ethylenediamine) cobalt (III) Bromide*

[Coen,S04]Br
From a burette 27.0ml of 1.00Af sulfuric acid are added
to a solution of 4.3g of the carbonatobromide (127 b) in
85ml of water. The red solution is evaporated to a very
viscous residue on the steam bath. After triturating with
methanol in a mortar, the violet product, now in the form
of a fine powder, is filtered and rinsed with acetone.
Yield, quantitative
Reference: DUFF, J. Chem. Soc, 453 (1922).

128. Carbonatotetramminecobalt (III)

Nitrate y2-Hydrate *
2Co(NO,)2 + 6NH, + 2(NH4)2CO, + ttO, ►

2Co(NH,)4CO,NO, + 2NH4NO, + H20

One hundred grams of cobalt (II) nitrate 6-hydrate are

dissolved in 100ml of hot water; or 40g of cobalt carbonate
are added in portions to a mixture of 50ml of concentrated
nitric acid and 50ml of water. The filtered cobalt solution is
added to a mixture of 200g of ammonium carbonate in one
liter of water and 500ml of concentrated aqueous ammonia.
The resulting liquid is transferred to a 2-liter suction flask
fitted with a stopper and an inlet tube which reaches almost
to the bottom of the vessel. Air is drawn through the deep
 Inorganic Laboratory Preparations

violet solution for 3 hours after which time the color has
become dark red.
Alternatively, the reaction mixture may be rapidly oxi
dized by cooling it to 10°C in an ice bath and adding 25ml
of 30% hydrogen peroxide slowly from a burette with con
tinued cooling and agitation. The solution from the peroxide
oxidation is allowed to stand for 10-20 minutes and then
worked up as follows.
The dark red liquid is evaporated on the steam bath to a
volume of 500ml while 10g of solid ammonium carbonate
are added every 30 minutes. Any black cobaltic oxide that
may form is filtered off by suction while the solution is hot
and it is then further concentrated to 350ml. The addition
of ammonium carbonate is continued during this time; the
overall time for the evaporation is 6-7 hours. After cooling
in ice, the red product is filtered and the filtrate is set aside.
The solid is washed with 75ml of 95% alcohol.

Yield = 48-58g

If the filtrate is evaporated to 100ml with addition of

ammonium carbonate, as before, and cooled in ice, 6-9g of
crude material is obtained.
This crop of crystals is contaminated with some car-
bonatopentammine nitrate which is removed by dissolving
the complex in 15 times its weight of water and adding 2-3
volumes of 95% alcohol.

*Yield = 5-7.5g
Overall Yield = 56-63g

Reference: I, vol. 6:173.

Cognate Preparations

128a. Chloride*
[Co(NH2)4CO,]CI

Forty grams of cobalt carbonate are combined with a

mixture of concentrated hydrochloric acid and 40ml of
water are used; or a solution of 80g of cobalt chloride
6-hydrate in 100ml of hot water. The oxidized solution is
 Coordination Complexes 233

evaporated similarly to the nitrate until the volume is 500ml

and then 1250ml of alcohol are added. After cooling in ice,
the salt is filtered off and washed, first with 50% alcohol,
then with 95% alcohol.

Yield = 48-50g

128 b. Sulfate (3-Hydrate) *

[Co(NHa)4COt],SCV3HaO

This compound is prepared from 40g of cobalt carbonate

and 20ml of concentrated sulfuric acid in 130ml of water;
or from 94g of cobalt sulfate 7-hydrate in 150ml of water.
The procedure is the same as for the nitrate.

Yield = 60-64g
The bromide, iodide, and oxalate may all be prepared
similarly by using ys mole of the corresponding cobalt salt
or 40g of the carbonate dissolved in the equivalent amount
of dilute acid.
References:
1. B:172; J:378.
2. Vortmann, Ber., 10:1456 (1877).
3. Vortmann and Blasberg, Ibid., 22:2648 (1889).
4. Jorgensen, Z. anorg. Chem., 2:279-283 (1892).

1 28c. Chloroaquotetramminecobalt (III) Sulfate*

[Co(NH,)4(H.O)CI]S04
[Co(NH,),CO,CI + 2HCI ► [Co(NH,)4(H.O)CI]CI. + CO,
[Co(NH,).(H,O)CI]CI, + H,SO4 ► [Co(NH,)4(HtO)CI]SO, + 2HCI

Twenty grams of cobalt carbonate are dissolved in a mix

ture of 30ml of concentrated hydrochloric acid and an equal
volume of water; or 40g of cobalt (II) chloride 6-hydrate
in 60ml of water are used. The cobalt solution is added to a
mixture of 100g of ammonium carbonate in 300ml of water
and 250ml of concentrated aqueous ammonia. The entire
mixture is oxidized with air for two hours, or treated drop-
wise with 10ml of 30% hydrogen peroxide at 10°C.
While the liquid is evaporating to 200ml on the steam
bath, 5g of solid ammonium carbonate is added every 20-30
minutes. The solution is filtered hot to remove any cobalt
 Coordination Complexes 241

131 e. Chloro(anilino) bit (ethylenedlamine) cobalt (III)

Chloride*
[Coena(CtH,NHa)CI]C!a

Five grams of neutral fr-dichloro chloride are stirred to

a smooth paste with 5ml of water, and 5ml of pure aniline
are added. The mixture is allowed to stand for one hour;
the color changes from green to red and the reaction mix
ture almost solidifies. The material is triturated with meth
anol to a light-red powder, filtered, and washed with ether.
The yield is almost quantitative.
The p-toluidine homologue is produced similarly from 5g
of the complex, 2g of the amine, and 3ml of water. After
standing for two days, during which time any large par
ticles that form must be ground up, the material is isolated
as described.

Reference: GMELIN, Handbuch der Anorganischen Chemie, No. 58B,

Verlsg Chemie, Berlin, 1930.

132. cis- and trans-Dichlorotetramminecobalt (III)

Chloride **
alcohol
eia Form: [Co(NH,)4CO,]CI + 2HCI ► e,a-[Co(NH,)4Cl,]CI + CO, + H.O

One hundred milliliters of absolute ethyl alcohol are

placed in a gas-absorption flask and saturated at 0°C with
hydrogen chloride under the hood. Eighty grams of this
solution is shaken with 40g of finely powdered carbonato-
tetramminecobalt (III) chloride (No. 128 a) at room tem
perature until the evolution of carbon dioxide is complete.
The gray-blue solid is immediately filtered off and washed
with 100ml of absolute alcohol. A pale violet powdery solid
remains which is dried in vacuo over alkali.

Yield quantitative (as the Vfc-hydrate)

The purification of the salt is tedious and attended by
considerable loss, but it may be carried out as follows :
Five grams of the crude product is leached on the filter
with about 5-10ml of ice-cold water. Any frans-dichloro
material remains behind and the filtrate is run directly onto
242 Inorganic Laboratory Preparations

4-5g of very finely powdered sodium dithionate 2-hydrate

(see No. 47). The violet mixture is stirred until no more
precipitate of the pale-purple dithionate forms. The latter
is separated from the denser excess of sodium dithionate
by making a slurry with a few ml of ice-water, and then
filtered. Even with rapid work, only about 2g of cis-
[Co(NH3)4Cl2]2S2Oa is obtained, because of attendant hy
drolysis of the cation to the chloroaquo salt.
The dithionate precipitate then obtained is ground in a
mortar with 4g of ammonium chloride and 4ml of water
until the salt has become dark blue. The solids are filtered
off and treated dropwise with ice-cold water until, with con
tinued stirring, no more crystals of NH4Cl are noticeable.
The pale blue supernatant liquid is decanted; as long as
ammonium chloride is present, the desired product is vir
tually insoluble in water. The solid is stirred with 5ml of
ice-cold water until it dissolves and is then instantly suc
tion-filtered into a slurry of 5g of ammonium chloride in
5ml of water. The reprecipitated complex chloride is freed
from the denser NH4Cl by gently swirling and is filtered off.
It is freed from contaminating salt by moistening it on a
clay plate with two successive 1ml portions of ice water,
pressing the violet-blue product well dry each time.

Yield 1-1.5g
Reference: Werner, Ann., 386:103 (1912); Ber., 40:4821 (1907).
fron2-Form: [Co(NH,)4(H.O)CI]SO4 + HCI ► [Co(NH,)4CI,]HSO4 + H,O

frans-[Co(NH,)4CI,]HSO4 + HCI ► fron2-[Co(NH,)4CI,]CI + H,SO,

(I)
Five grams of chloroaquotetramminecobalt (III) sulfate
(No. 128 c) are added to 25ml of concentrated sulfuric acid
and the mixture is allowed to stand two to three hours at
room temperature. The violet solution is cooled in ice and
25ml of concentrated hydrochloric acid are added slowly
from a tap-funnel under the hood. [CAUTION: Gloves
should be worn during this operation as much hydrogen
chloride is evolved.] After standing overnight in a stop
pered flask at normal temperature, the almost colorless
supernatant liquid is decanted from the green solid. The