ethylenediamine and dimethylglyoxime are hidentate ligands,

and they form complexes with Ni(III2+which are widely different in terms of color, geometry and stahility. In this demonstration color differences and relative stabilities are observed; the instructor must provide students with the additional information presented later on in this section.
'I'he rhuice ut pnx:e(luw dqwnds on the visual impart desired and the rmsons for ~erforming:the demonstration. Only
procedure B shows the three different complexes with ethylenediamine. If procedure A were to be modified in an attempt
to show the colors of the three complexes with ethylenediamine, the intense hlue color of Ni(NH3k2+ would cause
complications. However, the sequence in procedure A is based
on the relative stability of the different complexes and can he
used for that purpose. Procedure C allows for observing color
changes upon addition of different reagents in the specified
sequence.
The following equations represent the chemical changes
observed in alternate procedure B (en = ethylenediamine, H2NCH2CH2NH2, dmg = dimethylglyoxime,
CH3-C-C-CH3

I1 I1

HO-N

In all three procedures the most stable species of nickel(I1)

is Ni(CN)d2- and that, along with relative dissociation and
solubility of the other species, is the basis for the suggested
sequences of mixing.
The color, geometry and formation constants4 for the
complex ions are shown below:
Formula

Ni(H20)s2+

green

Ni(NHa)sZt

deep blue
light blue
blue
purple
red
yellow

[Ni(HzO)den)12+
[Ni(H@)2(enl.12+
Ni(en)32t
Ni(dmg).
Ni(CN)42-

Kf, 25C

Geometry

Color

octahedral
octahedral
octahedral
octahedral
octahedral

6.46 X 1O8(30"CI
3.55 x 10'
5.62 x

square planar
square planar

3.31 X 10"
4.17 X 10"
3.16 X 1030

The geometric structures of the complex ions are:

1. Hexaaquoniekel (11)ion: Ni(Hz0)P

N-OH
Ni(Hp0)P + 6NHl- Ni(NHdgZ++ 6H20
green
deep blue
Ni(HzO)QLt+ en -INi(H20)~(en)12++ 2H20
green
light blue
Ni(Hz0)eZ++ 2en -[Ni(H20)2(en)z12+ + 4H20
green
blue
Ni(Hz0)e2+ 3en -nI(en)s2+ + 6Hz0
green
purple
Ni(H20)s2++ 2dmg -Ni(dmg)a + 6Hz0 + 2H+
green
red
Ni(Hz0)~~+
+ 4CN--Ni(CN)a2- + 6Hz0
green
yellow
When excess cyanide ion solution is added to a solution containine nickel (11) the final oroduct is Ni(CN)a2-. Invariablv.
is ohserved hefbre all the cyathe formation o f a
nide ion solution is added. The identity of this precipitate,
presumably Ni(OH)z, Ni(CN)2 or Ni[Ni(CN)4], which dissolves auicklv uDon addition of excess cvanide ion solution,
is not ciear. cbnfiicting literature values a;e reported by Gayer
and Garrett1 (at 25'C K,, for Ni(OH)2 = 6.5 X lo@), Hume
and
and KolthofP (at 25'C K,, for Ni(Ni(CN)4] = 1.7 X
Linke3 (at 25'C K., for Ni(OH)2 = 1.6 X 10-"j, K., for
Ni(CN)2 = 2.21 X 10-12).
The K., value4 for the insoluble red complex formed hetween nickel 111)
is 2.1 X lo-" a t 25C.
. . and dimethvlelvoxime
.. .
Since the value" olthe furmarim ronstant, Ki, for thec~mplex
N i ~ d m e his 4.17 X 10". the intriniir soluhilitv constant. K..
of the complex can he calculated to he 8.8 X CO-~.

OH,
2. Hexaamminenickel (11) ion: Ni(NH3)2*
NH.

3. Tetraaquoethylenediamineniekel(11) ion: [Ni(H20)r(en)J2+

OH,
4. Diaquohis(ethylenediamine)nickel(~)ion: [Ni(H20)den)2I2+
HS

Note that, in theory, cis-trans isomers are possible as well as optical

isomers for the cis configuration
5. Tris(ethy1enediamine)nickel (11) ion: Ni(en)s2+

~~

Note that, in theory, optical isomers are possible.

6. Bis(dimethylglyoximato)niekel (11):Ni(dmg)p

'Gayer, K. H., and Garrett, A. B.. J. Amer. Chem. Soc., 71,2973

(1949).
Hume, D. N., and Kolthoff, I. M., J Amer Chem. Soe., 72,4423
(1950).
3 Linke, W. F., "Solubility of Inorganic and Metal-Organic Compounds," Vol. 2.4th Ed., American Chemical Society, Washington,
D.c.,1965.
Sillen, L. G., and Martell, A. E., "Stability Constants of Metal-Ion
Complexes," Special Publication No. 25, Supplement No. 1, The
Chemical Society (London),1971.

The geometry of this coordination compound is square planar

7. Tetracyanonickelate(I1)ion: Ni(CN)F

NciBcN
NC

CN

Volume 57. Number 12, December 1980 1 901