Coordination Complexes of Cobalt

Inorganic Synthesis in the General Chemistry Laboratory

Gregwy M. Williams, John Olmsted Ill, and Andrew P. Breksa Ill
~aliforniaState University, Fullerton, Fullerton, CA 92634

The American Chemical Societv has established puide- One of the six ligands in the octahedral system is suhstan-
lines for undergraduate educatio; calling for an increased < -
tiallv more labile than the other five. makinn i t oossihle
carry out displacement reactions 6 generate the various
~~~ ~ ~ ~~ ~
to-
emohasis on inorganic and descriptive chemistry. One possi-
ble'way of implementing these changes in our &rricula is to pentamine complexes:
reorganize the general chemistry sequence. By necessity,
this approach will also require a revision of the introductory
laboratory. Typically, laboratory experiments in general In this equation, q denotes t h e charge on the ligand L. In the
chemistrv
.------
~ emohasize
~ *~
~ ~ -nhvsical
"
~ ~ d
.
and analvtical methods. T o
the student, this frequently translates into a seemingly eud-
preparations described here, q = 0 (HzO, N H d or q = -1
(ONO-, NOz-, c1-).
less series of titrations leadine to extensive and tedious cal- . . .oentamine comolexes are eenerallr rather
While Co(II1)
culations. General chemistr;lahoratories suffer from the soluble in water, their chloride saits can be from
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- +
~ [ C O ( N H , ) , L ] ' ~ + ~+' +(3( ~ ~q)CL-(aq,
) excess)
ing more chemical synthesis into the introductory lahorato-
ry. Syntheses of coordination complexes are particularly at-
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
varietv of hiehlv colored comoounds. Several exoeriments ions (H30+, OH-), the resulting solid products are suffi-
on coordinaGon chemistry hake appeared in this Journal; ciently pure that recrystallization or other purification
most of these have emphasized the chemistry of Co(II1). methods are unnecessary.
Sehera (I) 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(II1) comdexes are orepared and studied. There
have also been reports on th; synthesis of optically active All procedures were adapted from either Schlessinger (17)
Co(II1) complexes (5,6), and there are brief descriptions of or Jolly (18).
thesynthesesof [Co(NH3)~CI]CIz(7). [Co(en)zClz]C1(8),and 1. Spthesis of [WNH3)5CI]CIz
[Co(en)a]s (9). One paper concerns a number of metal acetyl- In a fume h o d , add 10g of ammonium chloride to 60 mL concen-
acetonate complexes (lo), and experiments concerning Ni trated aqueous ammonia in a 250-mL Erlenmeyer flask. (The com-
(11,12), Fe (13,14), and Cu (1616) have appeared. Most of bination of NH&l and NHdaq) guarantees a large excess of the
these papers describe the synthesis of just one or two com- NH3ligand.) 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 CaCLz.
paper, we describe a n experiment involving synthesis and 6H20in small portions. Next, add 16 mL 30%hydrogen peroxide to
spectral studies of a series of [Co(NH&L] complexes (L = the brown Co slurry, using a buret that has been set up in the hood
NH3, Cl-, H20, NOz-, and ONO-) that not only gives gener- and filled by the laboratory instructor. An addition rate of about 2
al chemistry students a n introduction to inorganic synthesis drops per second is usually sufficient, hut care should he taken to
hut also allows them to conduct a systematic study on the avoid excessive effervescence in this exothermic reaction. (If 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-
Background
tion.) When the effervescence has ceased, add 60 mL conc. HCl with
continuous stirring, pouring about 1-2 mL at a time. At this point,
The preparation of Co(II1) pentamine complexes is car- thereaction may he removed from the hood. Use a Bunsen burner to
ried out most conveniently starting from CoC12 6Hz0, . heat the solution to 60 "C with occasional stirring. Hold the tem-
perature between 55 OC and 65 'C for 15min; this incubation period
which is both inexpensive and quite stable. The first step in
the syntheses of these complexes requires oxidation t o con- is necessary to allow complete displacementof all aquo ligands. Add
50. mL deionized water. and allow the solution to cool to room
vert the metal from the +2 to the +3 oxidation state. The ~~~~ ~ ~

oxidation reaction is best carried out using concentrated temperature. Collect the purple product hy filtration through a
Burhner funnel, wnsh rt three times with 15 ml. cold deionized
Hz02 in basic ammoniacal solution. Hydrogen peroxide as an water and twice wrth 15 mL ice.cdd 95'3 ethanol. (The solutims
oxidizing agent generates only OH- as reduced product, and must be cold IO prevent undue lols of product hy rediasulving.)
the presence of ammonia guarantees that the Co3+ will he Transfer the product to a rrvstalli~ingdish, loosely rover with A1
stabilized immediately by formation of amine complex(es). foil, and nilow to drv until the following laboratory pericld.
(The Co3+ ion is not stable in aqueous media since i t forms caution: 30%hybrogen peroxide is strong oxidizing agent that
the strongly oxidizing hexaquo complex.) will cause severe burns and bleaching of skin and clothing. Burets
H,Oz(aq) + 2e- -- 20H-
2C03++ 2e-
should only be filled by qualified laboratory instructors, and stu-
dents should he warned of the potential hazards of this reagent.

Net:
2C02+
2C03+ 12NH3
2C02++ HzOz+ 12NH3
+ -- 2[Co(NH3)J3+
+
2[Co(NH3)J3' 20H-
2. Synthesis of [Co(NH3)dH&)]C13
Place 5.0 g uf [Co(NH1),CI]CI0~nn 2M.rnL Erlenmeyer flask,and
add 75 mI. of 5%aqueous nmrnmia. (L's~ngaqueous ammonla as the

Volume 66 Number 12 December 1989 1043

solvent prevents displacement of the N& ligands.) Heat on a hot coordination compounds are not the "colors" of the ah-
plate in the hood until the compound dissolves. Cool the solution to sorhed light.
10 'C 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 HCL dropwise with stirring until
a red precipitate appears and a fog (ammonium chloride vapor) no theses. Instruetors may wish to elaborate on the chemical
longer forms above the solution. (Under these conditions ligand principles involved, particularly if the experiment is carried
exchange between [Co(NH3)sC1I2+and [ C O ( N H ~ ) ~ H ~isOvery ]~+ 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 heen covered, the oxida-
because it is much less soluhle than is the cNoro dichloride.) Cool tion step and the relative instability of [Co(HzO)s13+can he
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 i t can merely he pointed out that the cohalt 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
concepts have already been introduced, the displacement,
3. Synthesis of [Co(NH3),0NO] C12
precipitation, and isomerization reactions can he descrihed
Dissolve 5.0 g of [Co(NH3)sCI]Chin 75 mL of 10%aqueous ammo- using these concepts, particularly Le Chatelier's principle. If
nia in a 250-mL Erlenmeyer flask on a hat plate in the haod. Stir the experiment is done before equilibrium ideas have heen
with a metal spatula. Cool the solution to about 10 "C in an ice hath,
then add 2.0 M HCI until the solution is neutral to litmus. (The use developed, these same reactions can be treated as though
of 2 M HCI rather than eonc. HCI (synthesis 2) dilutes the solution they proceed to completion. For more sophisticated stu-
sufficientlythat 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 HCl. Allow the reaction mixture to kinetic and thermodynamic control of reaction products as
stand in an ice hath for at least an hour. Filter through a Buchner
funnel, then wash the yellow-arange 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. Physlcal Properties of the Cobalt Complexes

4. Synthesis of [WNH3)f102] C12 Complex Color Transition Energy

Dissolve 3.0 g of the nitrito isomer [Co(NH3)sONO]CIzin 30 mL
hot water containine 6.0 mL conc. aoueous ammonia. Cool the LCo(NHs)sCIICl~ Purple 530 nm 225 kjlmol
solution in an ice hati..and add 30 mL e&. HCL. Allow the mixture
~
~ ~ ~~ ~ ~~ ~~~~~
~Co(NH~16H201Cls Red 495 nm 240 kjfmol
t o stand in the ire hath until precipitation is complete. Collect the [Co(NHs)sONO]C1~ Yellow-Orange 485 nm 245 kjlmol
product by filtration through a Burhner funnel. and wash the pale [Co(NHd~NH~ICI~Orange 475 nm 250 kjlmol
solid with 25 mL cold Y5%ethanol.All~cvthe product to air-dry. [Co(NH&NO.ICi~ Orange 460 nm 260 kjlmol

5. Synthesis of [Co(NH3),] GI3

Add 5.0 g of CoCll. 6H20 and 3.3 g of NH&l to 30 mL water in a
250-mL Erlenmeyer flask. In the hood add 1.0 g activated charcoal
and 45 ml. mnc. aqueous ammonia. Cod the brown slurry in an rce
bath to 0 ' C , then add 4.0 mL :iU0'o HIOI from a hwet na described
for thewnthes~sofICO(NHI).CIICI. . . .Do not allow the temwrature
to rise above 10 'C. Heit the resulting red-brown solution 60 OC,
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 T; 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 conc. HCI. Heat the mixture to 70 "C, and filter
while still hot. Place the filtrate in an ice hath, and add 1.0 mL cold
cane. HCI. Collect the orange solid by filtration, wash with 25 mL
ice-cold 95%ethanol, and allow to air-dry.
Figure 1. Visible specba of [CO(NH.)~H.O]~+
-( ) [Co(NHd&1I2+
Discussion (........).and [Co(NH&NHs13+(- - - - -).
These syntheses can he completed in four 3-h laboratory

1
sessions. During the first period [Co(NH3)&1]C12 is pre-
pared, and i t is used in the next lahoratorv session for the
synthesis of the aquo and nitrito derivatives. The final two
periods leave sufficient time to conduct the nitrito-nitro
isomerizationand to prepare the hexamine CIS'' salt. Viaihle
spectra for all of the components, recorded as dilute aqueous
solutions on a Beckman DU-7 or other recordine soertro-
photometer, can he collected over the course of t i e kxperi-
ment. It is important to obtain the spectrum of [Co-
ext. 600
(NH3)50NO]C12immediately after isolation since this com- [Co(NH,),ONOlz*
coeff.
pound isomerizes to the nitro derivative rather quickly a t
room temperature. The other four compounds are quite sta- 400 , \
ble; their spectra may he recorded as time permits.
\
The visible spectra of all five of the cobalt complexes are 200 \
\
displayed in Figures 1 and 2. I n each case, ..,A is clearly
determined, allowing the students to verify thespectroche-
mical series (see table). I n most general chemistry textbooks 0
\
.L

the nitrito lieand is omitted from the snectrochemical series.

Thus, in adiition to illustrating the ebncept of linkage iso-
mers. ICO(NH&ONOIC~~ can act as an "unknown" in this
exercise. The & ~ e r i m ~ n i a l sreinforces
o the concept of ah- Figure 2. Visible specha of [Co(NH3)sONO]2t(-- ) and lCWH&-
sorbed vs. transmitted light. Clearly, the colors of these N0,l2+ (- - - -1. -
1044 Journal of Chemical Education
manifested by the synthesis of the nitrito comolex and its Literature Cited
eventual con;ersionb the nitro form.
Principles of stoichiometw can also hereinforced hv hav-
ing the students weigh the& products from each synthesis, I. Sebera. D. K. J. Chem.Edu, 1963.40.476,
compute the yield in each case (it should be clear to them 2. Wilson, L. R. J Chem.Educ. 1969,46,447.
3. Alexander, J. J.:Dorsey, J. 0.J. Chem. Educ. 1378.55.207-208
that the limiting reagent is always the cobalt starting materi- 4. Loehlin, J. H.; Kahl, S. B.: Darlington, J. A. J. Chem. Educ. 1982,59,104%1051.
al), and draw inferences about reaction efficiencies and 5. Hunt. H.R..h. J. ChamEduc. 1977,54,710-711.
6. Gargsllo, M. F.: Leehuga, L.: Puerla, M. C.; GonralwVilehw., F.; Vikplana, R. J.
causes of less than quantitative yields. With sufficiently Cham. Educ. 1988.65.101&1019.
careful technique, each of these syntheses has a yield in 7. Thieiman. V. J. Chem. Educ. 1974.51.536.
8. Leverett.P.;Oliver,M. J.J.Chem. Educ. I976,53,440.
excess of 90'3, but there are ample opportunities for less 9. Krauae, R. A ; M e g q l e , E. A. J. Cham. Educ. 1976.53,667.
skilled experimentalists to lose significant amounts of their 10. Glidewell, C.: McKechnie,J. S, J. Chem. Educ. 1988,65,10lC1017.
products. 11. Filgueiraa,C.A. L.;Cara%za,F.J. Chem.Edue. 1980.67,18261827.
12. Wieder.G. M. J.Chem.Educ. 1986,53,988-999.
This was the first opportunity for many of the students 13. Bmok8.D. W.J.Chem.Educ. 1973,50,218.
actuallv to isolate comnounds. and in this exneriment the 14. Olmsted, J.. 111. J. Chem. Edue. 1984.61. 109MW9.
15. O'Brien, P. J. Chem. Educ. 1982,59,1052-1053.
inherent rewardsofchemical syntheaisare multiplied by the 16. Potta,R.A. J. ChemEduc. 137451,539-540.
visual a w e d of the chemistw. Most of the students io the 17. Sehlessinger. 0. G. I w ~ g a n i cLnborotory Preporofiona; Chemical Publishing- New
York, 1962.
class enjoyed this experimentvery much; several felt that it 18. Jolly. W.L. TheSynfheskand Chomcfrrizotion oflwrgonic Compounds: Prentim-
was the best laboratory exercise of the year. Hall: E n g e l d Cliffs, NJ, 1970: p 461.

Volume 66 Number 12 December 1989 1045