1

Linkage Isomers: Synthesis and Characterization of

[Co(NH
3
)
5
ONO]Cl
2
and [Co(NH
3
)
5
NO
2
]Cl
2

Divalent cobalt is more stable than trivalent cobalt for simple salts of cobalt, with only a
few salts of Co(III) known (e.g. CoF
3
). Formation of a coordination complex stabilizes a
higher oxidation state as evidenced by a number of octahedrally coordinated complexes.
In this experiment, you will prepare two linkage isomer compounds,
[Co(NH
3
)
5
ONO]Cl
2
and [Co(NH
3
)
5
NO
2
]Cl
2
.

1) The synthesis of [Co(NH
3
)
4
CO
3
]NO
3
involves the following unbalanced equation,

Co(NO
3
)
2
+ NH
3
(aq) + (NH
4
)
2
CO
3
+ H
2
O
2
[Co(NH
3
)
4
CO
3
]NO
3
+ NH
4
NO
3
+ H
2
O

Cobalt nitrate [Co(NO
3
)
2
]

is deliquescent (tends to absorb atmospheric water vapor and
become liquid). Upon exposure to atmospheric moisture, cobalt nitrate has the formula
Co(NO
3
)
2
6H
2
O.

Co(II) complexes react very rapidly by ligand exchange, thus a possible first step in the
reaction:

Co(OH
2
)
6
2+

+ 4NH
3
(aq) + CO
3
2-

Co(NH
3
)
4
CO
3
+ 6H
2
O

Which could then be oxidized by addition of H
2
O
2
to form [Co(NH
3
)
4
CO
3
]
+
.

2) One synthesis scheme of [Co(NH
3
)
5
Cl]Cl
2
involves the following equations,

[Co(NH
3
)
4
CO
3
]
+
+ 2HCl [Co(NH
3
)
4
(OH
2
)Cl]
2+
+ CO
2
(g) + Cl
-

[Co(NH
3
)
4
(OH
2
)Cl]
2+
+ NH
3
(aq) [Co(NH
3
)
5
(OH
2
)]
3+
+ Cl
-

[Co(NH
3
)
5
(OH
2
)]
3+
+ 3HCl [Co(NH
3
)
5
Cl]Cl
2
(s) + H
2
O + 3H
+




[Adapted From: Tanaka, J. and Suib, S.L.. Experimental Methods in Inorganic Chemistry; Prentice-Hall: 1999 and
Jolly, W.L. The Synthesis and Characterization of Inorganic Compounds Prentice-Hal: 1970.]
2
3) Synthesis of [Co(NH
3
)
5
ONO]Cl
2
and [Co(NH
3
)
5
NO
2
]Cl
2
involves the following:


[Co(NH
3
)
5
Cl]
2+
+ H
2
O [Co(NH
3
)
5
H
2
O]
3+
+ Cl
-


[Co(NH
3
)
5
H
2
O]
3+
+ NO
2
-
[Co(NH
3
)
5
ONO]
2+
+ H
2
O

[Co(NH
3
)
5
ONO]
2+
[Co(NH
3
)
5
NO
2
]
2+


Synthesis and Experimental Procedure:

Chloropentaamminecobalt(III) chloride, [Co(NH
3
)
5
Cl]Cl
2

Make a solution of 5.0 g ammonium chloride NH
4
Cl

in 30 mL of concentrated aqueous
ammonia in a 250 mL Erlenmeyer flask. While stirring with magnetic stirbar, slowly add
10 g of cobalt(II) chloride hexahydrate. While continuously stirring, slowly add 8 mL of a
30% H
2
O
2

solution (CAUTION: H
2
O
2
is a strong oxidizing agent that can cause severe
burns. Use gloves! Wash affected areas immediately with water!). When evidence of
further reaction has ceased, slowly add 30 mL of concentrated HCl. Heat the solution
using a hot plate in a fume hood. Maintain a temperature of about 85C for about 20
minutes. Do not allow the solution to boil. Cool the solution slightly and then place in an
ice water bath. Isolate the crystalline product by suction filtration. Wash the product with
a small amount of ice-cold water. The total volume of the wash should not exceed 15 mL.
Wash with 15 mL of cold 6M HCl. Allow the product to dry on the filter paper and then
weigh the product to determine the approximate yield. Discard the filtrate wash solution
in the in the appropriate cobalt waste containers in the fume hood.

Pentaamminenitritocobalt(III) chloride, [Co(NH
3
)
5
ONO]Cl
2

Heat a solution (do not boil) of 8 mL of concentrated aqueous ammonia in 80 mL of
water. While heating and stirring, add 5.0 g of dry [Co(NH
3
)
5
Cl]Cl
2

or 6.0 g wet
[Co(NH
3
)
5
Cl]Cl
2
. Continue heating, below boiling point, and stirring until the product
dissolves. This may take 15 minutes or more. If you observe the presence of a dark
brown to black precipitate of cobalt oxide, filter it off. Cool the solution to about 10 C.
Add 2 M HCl slowly while keeping the solution cold until it is neutral as determined by
litmus or pH paper. Add 5.0 g of sodium nitrite followed by 5 mL of 6 M HCl. Cool the
solution in an ice bath for approximately an hour, then filter the precipitated salmon pink
crystals of [Co(NH
3
)
5
ONO]Cl
2
. Wash with 20 mL of icewater then 20 mL of 95%
3
ethanol. Allow it to dry on the lab bench for approximately one hour before collecting
the IR and UV-Vis spectrum.

The product [Co(NH
3
)
5
ONO]Cl
2
is not stable and will isomerize to [Co(NH
3
)
5
NO
2
]Cl
2
.
Ensure you have sufficient time in the laboratory session to collect the IR spectrum of the
product on the same day as the synthesis.

Pentaamminenitrocobalt(III) chloride, [Co(NH
3
)
5
NO
2
]Cl
2

The product [Co(NH
3
)
5
ONO]Cl
2
will isomerize to [Co(NH
3
)
5
NO
2
]Cl
2
at room
temperature given sufficient time. The isomerization may also be facilitated by heating.
It is possible to use the [Co(NH
3
)
5
ONO]Cl
2
product before it is completely dry. Bring 20
mL of H
2
O to a boil and add a few drops of NH
4
OH. Turn off heat and allow cooling for
4 minutes after boiling has ceased. Add 2.0 g of [Co(NH
3
)
5
ONO]Cl
2
to the solution. As
this solution cools to room temperature, add 20 mL of concentrated HCl. After cooling
from solution, [Co(NH
3
)
5
NO
2
]Cl
2
will precipitate from solution. Filter the product from
solution and wash with small portions of a total of 10 mL 95% ethanol. Allow to dry
under vacuum for several minutes until dry and collect the IR spectrum and the UV-Vis
spectrum.

Ensure UV-visible and IR spectra have been collected for each of the three products,
[Co(NH
3
)
5
Cl]Cl
2
, [Co(NH
3
)
5
ONO]Cl
2
, and [Co(NH
3
)
5
NO
2
]Cl
2
.

Retain your products in labeled sample bags.