Coordination Complexes of Cobalt

Inorganic Synthesis in the General Chemistry Laboratory

Gregory M. Williams, John Olmsted III, and Andrew P. Breksa III
California State University, Fullerton, Fullerton, CA 92634

The American Chemical Society has established guide- One of the six ligands in the octahedral system is substan-
lines for undergraduate education calling for an increased tially more labile than the other five, making it possible to
emphasis on inorganic and descriptive chemistry. One possi- carry out displacement reactions to generate the various
ble way of implementing these changes in our curricula is to pentamine complexes:
reorganize the general chemistry sequence. By necessity,
this approach will also require a revision of the introductory [Co(NH3)5NH3]3+ + L1'(excess)
-
[Co(NH3)5L](3+,?)+ + NHa
laboratory. Typically, laboratory experiments in general In this equation, q denotes the charge on the ligand L. In the
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chemistry emphasize physical and analytical methods. To preparations described here, q 0 (H20, NH3) or q
=
1 = —

the student, this frequently translates into a seemingly end-

(ONO-, N02-, Cl-).
less series of titrations leading to extensive and tedious cal- While Co(III) pentamine complexes are generally rather
culations. General chemistry laboratories suffer from the soluble in water, their chloride salts can be precipitated from
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lack of visually exciting experiments that expose students to solution by excess HC1.
the full experience of chemistry.
These problems can, in part, be diminished by incorporat- 2[Co(NH3)5L]<3+"H(aq) + (3 + <j)Cl-(aq, excess)
ing more chemical synthesis into the introductory laborato- -*
ry. Syntheses of coordination complexes are particularly at- 2[Co(NH3)sL]Cl(3+?)(s)
tractive because they are easy to carry out in high yield, they If these reactions are carried out in aqueous media con-
involve relatively simple stoichiometries, and they provide a
taining only the ligands of interest and innocuous counter
variety of highly colored compounds. Several experiments ions (H30+, OH-), the resulting solid products are suffi-
on coordination chemistry have appeared in this Journal-,
most of these have emphasized the chemistry of Co(III). ciently pure that recrystallization or other purification
methods are unnecessary.
Sebera (1) and Wilson (2) published two of the earliest
experiments. More recently, Alexander and Dorsey (3) and
Loehlin et al. (4) described freshman laboratory projects in Experimental
which Co(III) complexes are prepared and studied. There
have also been reports on the synthesis of optically active All procedures were adapted from either Schlessinger (17)
Co(III) complexes (5, 6), and there are brief descriptions of
or Jolly (18).
the syntheses of [Co(NH3)5C1]C12 (7), [Co{en)2Cl2]Cl (8), and 1. Synthesis of [Co(NH3)5CI]Cl2
[Co(en)3]3 (9). One paper concerns a number of metal acetyl- a fume hood, add 10 g of ammonium chloride to 60 mL concen-
In
acetonate complexes (10), and experiments concerning Ni trated aqueous ammonia in a 250-mL Erlenmeyer flask. (The com-
(11,12), Fe (13,14), and Cu (15,16) have appeared. Most of bination of NH4CI and NH3(aq) guarantees a large excess of the
these papers describe the synthesis of just one or two com- NH3 ligand.) Stir the ammonium chloride solution vigorously using
pounds, and emphasize detailed characterization. In this a magnetic stirring plate while adding 20 g of finely divided C0CI2 •

paper, we describe an experiment involving synthesis and 6H20 in small portions. Next, add 16 mL 30% hydrogen peroxide to
spectral studies of a series of [Co(NH3)5L] complexes (L = the brown Co slurry, using a buret that has been set up in the hood
NH3, Cl-, H20, N02-, and ONO-) that not only gives gener- and filled by the laboratory instructor. An addition rate of about 2
al chemistry students an introduction to inorganic synthesis drops per second is usually sufficient, but care should be taken to
avoid excessive effervescence in this exothermic reaction. (If the
but also allows them to conduct a systematic study on the reaction shows signs of excessive effervescence, turning off the mag-
effect of different ligands on absorption spectra. netic stirrer momentarily will usually prevent overflow of the solu-
tion.) When the effervescence has ceased, add 60 mL cone. HC1 with
Background continuous stirring, pouring about 1-2 mL at a time. At this point,
The preparation of Co(III) pentamine complexes is car- the reaction may be removed from the hood. Use a Bunsen burner to
ried out most conveniently starting from CoCl2 6H20, •
heat the solution to 60 °C with occasional stirring. Hold the tem-
which is both inexpensive and quite stable. The first step in perature between 55 °C and 65 °C for 15 min; this incubation period
the syntheses of these complexes requires oxidation to con- is necessary to allow complete displacement of all aquo ligands. Add
vert the metal from the +2 to the +3 oxidation state. The 50 mL deionized water, and allow the solution to cool to room
oxidation reaction is best carried out using concentrated temperature. Collect the purple product by filtration through a
Buchner funnel; wash it three times with 15 mL cold deionized
H202 in basic ammoniacal solution. Hydrogen peroxide as an water and twice with 15 mL ice-cold 95% ethanol. (The solutions
oxidizing agent generates only OH- as reduced product, and must be cold to prevent undue loss of product by redissolving.)
the presence of ammonia guarantees that the Co3+ will be Transfer the product to a crystallizing dish, loosely cover with Al
stabilized immediately by formation of amine complex(es). foil, and allow to dry until the following laboratory period.
(The Co3+ ion is not stable in aqueous media since it forms Caution: 30% hydrogen peroxide is a strong oxidizing agent that
the strongly oxidizing hexaquo complex.) will cause severe burns and bleaching of skin and clothing. Burets
should only be filled by qualified laboratory instructors, and stu-
H202(aq) + 2e- — 20H- dents should be warned of the potential hazards of this reagent.
2Co2+ —
2Co'i+ + 2e-
2. Synthesis of [Co(NH3)JH20)]CI3
2Co3+ + 12NH3 —
2[Co(NH3)6]3+ Place 5.0 g of [Co(NH3)5Cl]Cl2 in a 250-mL Erlenmeyer flask, and
Net: 2Co2+ + H,02 + 12NH3 —
2[Co(NH3)6]3+ + 20H- add 75 mL of 5% aqueous ammonia. (Using aqueous ammonia as the

Volume 66 Number 12 December 1989 1043

solvent prevents displacement of the NH3 ligands.) Heat on a hot coordination compounds are not the “colors” of the ab-
plate in the hood until the compound dissolves. Cool the solution to sorbed light.
10 DC in an ice bath, then add a stirring bar, and place the flask on a
There is a great deal of chemistry involved in these syn-
magnetic stirrer. Add concentrated HC1 dropwise with stirring until theses. Instructors may wish to elaborate on the chemical
a red precipitate appears and a fog (ammonium chloride vapor) no
longer forms above the solution. (Under these conditions ligand principles involved, particularly if the experiment is carried
exchange between [Co(NH3)5Clp+ and [Co(NH3)5H20]3+ is very
out after these principles have been introduced in the lec-
rapid. The aquo trichloride complex is isolated by this procedure ture. If redox chemistry has already been covered, the oxida-
because it is much less soluble than is the chloro dichloride.) Cool tion step and the relative instability of [Co(H20)p,]3+ can be
the reaction mixture to below 10 °C, then collect the product by treated as practical examples of redox chemistry; otherwise,
filtration through a Buchner funnel. Wash the bright red solid twice it can merely be pointed out that the cobalt is being convert-
with 25 mL 95% ethanol, and allow it to dry in the air. ed from a lower to a higher oxidation state. If equilibrium
3. Synthesis of [Co(NH3)sONO]CI2 concepts have already been introduced, the displacement,
precipitation, and isomerization reactions can be described
Dissolve 5.0 g of [Co(NH3)5C!]Cl2 in 75 mL of 10% aqueous ammo-
nia in a 250-mL Erlenmeyer flask on a hot plate in the hood. Stir using these concepts, particularly Le Chatelier’s principle. If
the experiment is done before equilibrium ideas have been
with a metal spatula. Cool the solution to about 10 °C in an ice bath,
then add 2.0 M HC1 until the solution is neutral to litmus. (The use developed, these same reactions can be treated as though
of 2 M HC1 rather than cone. HC1 (synthesis 2) dilutes the solution they proceed to completion. For more sophisticated stu-
sufficiently that the aquo salt will not precipitate). Add 5.0 g sodium dents, it may be appropriate to note the differences between
nitrite followed by 5 mL of 6 M HC1. Allow the reaction mixture to kinetic and thermodynamic control of reaction products as
stand in an ice bath for at least an hour. Filter through a Buchner
funnel, then wash the yellow-orange solid with 25 mL cold water
and 25 mL cold 95% ethanol. Transfer the solid to a piece of filter
paper, and allow it to air-dry. Physical Properties of the Cobalt Complexes

4. Synthesis of [Co(NH3)sN02]Cl2 Complex Color a™, Transition Energy

Dissolve 3.0 g of the nitrito isomer [Co(NH3)5ONO]Cl2 in 30 mL
hot water containing 6.0 mL cone, aqueous ammonia. Cool the [Co(NH3)5CI]CI2 Purple 530 nm 225 kj/mol
solution in an ice bath, and add 30 mL cone. HC1. Allow the mixture [Co{NH3)5H20]CI3 Red 495 nm 240 kj/mol
to stand in the ice bath until precipitation is complete. Collect the [Co(NH3)5ONO]CI2 Yellow-Orange 485 nm 245 kj/mol
product by filtration through a Buchner funnel, and wash the pale [Co(NH3)sNH3]C!3 Orange 475 nm 250 kj/mol
solid with 25 mL cold 95% ethanol. Allow the product to air-dry. [Co(NH3)5N02]CI2 Orange 460 nm 260 kj/mol

5. Synthesis of {Co(NH3)e\Ci3
Add 5.0 g of CoCl2 6H20 and 3.3 g of NH^Cl to 30 mL water in a
•

250-mL Erlenmeyer flask. In the hood add 1.0 g activated charcoal

and 45 mL cone, aqueous ammonia. Cool the brown slurry in an ice
bath to 0 °C, then add 4.0 mL 30% H20-2 from a buret as described
for the synthesis of [Co(NH3)5Cl]Cl2. Do not allow the temperature
to rise above 10 °C. Heat the resulting red-brown solution to 60 °C,
and maintain this temperature for 30 min. (The incubation is need-
ed to ensure complete displacement of all aquo ligands.) Cool the
mixture to 0 °C; the product will precipitate from the solution.
Collect the product and the charcoal by filtration. Recrystallization
is necessary to separate the product from the activated charcoal.
Place the solid in a 250-mL Erlenmeyer flask, and add 40 mL hot
water and 1.0 mL cone. HC1. Heat the mixture to 70 °C, and filter
while still hot. Place the filtrate in an ice bath, and add 1.0 mL cold
cone. HC1. Collect the orange solid by filtration, wash with 25 mL wavelength,nm
ice-cold 95% ethanol, and allow to air-dry.
Figure t. Visible spectra of [Co(NH3)5H20]3+ (-) [Co(NH3)5Cl]2+
Discussion (........),and [Co(tJH3)5NH3]3+ <-----).

These syntheses can be completed in four 3-h laboratory

sessions. During tbe first period [Co(NH3)5Cl]Cl2 is pre-
pared, and it is used in the next laboratory session for the
synthesis of the aquo and nitrito derivatives. The final two
periods leave sufficient time to conduct the nitrito- -nitro
isomerization and to prepare the hexamine Co3+ salt. Visible
spectra for all of the components, recorded as dilute aqueous
solutions on aBeckman DU-7 or other recording spectro-
photometer, can be collected over the course of the experi-
ment. It is important to obtain the spectrum of [Co-
(NH3)sONOjCl2 immediately after isolation since this com-
pound isomerizes to the nitro derivative rather quickly at
room temperature. The other four compounds are quite sta-
ble; their spectra may be recorded as time permits.
The visible spectra of all five of the cobalt complexes are
displayed in Figures 1 and 2. In each case, Amax is clearly
determined, allowing the students to verify the spectroche-
mical series (see table). In most general chemistry textbooks
the nitrito ligand is omitted from the spectrochemical series. 400 450 500 550 600 650
Thus, in addition to illustrating the concept of linkage iso- wavelength.nm
mers, [Co(NH3)gONO]Cl2 can act as an “unknown” in this
exercise. The experiment also reinforces the concept of ab- Figure 2. Visible spectra of [Co(NH3)6ONO]2+ (-) and [Co(NH3)5-
sorbed vs. transmitted light. Clearly, the colors of these NOs]2+(-----).

1044 Journal of Chemical Education

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eventual conversion to the nitro form.
Principles of stoichiometry can also be reinforced by hav-
ing the students weigh their products from each synthesis, 1. Sebera, D, K. J. Chem. Educ. 1963,40,476,
Wilson, L. R. J. Chem. Educ. 1969,46,447.
compute the yield in each case (it should be clear to them 2.
3. Alexander, J. J.; Dorsey, J. G. J. Chem. Educ. 1978,55, 207-208.
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causes of less than quantitative yields. With sufficiently Chem. Educ. 1988,65, 1018-1019.
careful technique, each of these syntheses has a yield in 7. Thielman, V, J. Chem. Educ. 1974,51, 536.
excess of 90%, but there are ample opportunities for less
8. Leverett, P.; Oliver, M. J. J. Chem. Educ. 1976,53,440.
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skilled experimentalists to lose significant amounts of their 10. Glidewell, C.; McKechnie, J. S. J. Chem. Educ. 1988,65, 1015-1017.
products. 11. Filgueiras, C. A. L.; Carazza, F. J. Chem. Educ. 1980,57, 1826-1827.
12. Wieder, G. M. J. Chem. Educ. 1986,63,988-999.
This was the first opportunity for many of the students 13. Brooks, D. W. J. Chem. Educ. 1973,50, 218.
Olmsted, J., III. J. Chem. Educ. 1984, 61,1098-1099.
actually to isolate compounds, and in this experiment the 14.
15. O’Brien, P. J. Chem. Educ. 1982,59,1052-1053.
inherent rewards of chemical synthesis are multiplied by the 16. Potts, R. A. J. Chem. Educ. 1974,51, 539-540.
visual appeal of the chemistry. Most of the students in the 17. Schlessinger, G. G. Inorganic Laboratory Preparations; Chemical Publishing: New
class enjoyed this experiment very much; several felt that it York, 1962.
18. Jolly, W. L. The Synthesis and Characterization of Inorganic Compounds; Prentice-
was the best laboratory exercise of the year. Hall: Engelwood Cliffs, NJ, 1970; p 461.

Volume 66 Number 12 December 1989 1045