Name: Aditya Gaur

Id No. 2014B2A2585P

TITLE: Illustration of Jahn Teller Effect using complexes

of Ni+2 and Cu+2 with ethylenediamine.

OBJECTIVES:-
(1.) Measuring heat evolved when aqueous Ni+2 & Cu+2 ions
react with increments of en using a coffee cup calorimeter.
(2.) Determine the maximum number of ethylenediamine (en)
ligands that bind to a Cu+2 ion in aqueous solution by using
measurements from (1.).
(3.) Performing Computational study using Molden, Q-chem &
other software to support experimental findings.
(4.) Recording the UV-Vis spectra of the en complexes of Ni+2
and Cu+2.

SUMMERY:-
In 1937, Hermann Jahn and Edward Teller postulated a theorem
which stated that "stability and degeneracy are not possible
simultaneously unless the molecule is a linear one," in regards
with its electronic state.
The Jahn-Teller effect is a geometric distortion which reduces
symmetry and energy of a non-linear molecular system.
Both Ni+2 and Cu+2 bind with 6 ligands (water molecules) to
form [Ni(H2O)6]+2 and [Cu(H2O)6]+2 respectively. The structures
of both these are as shown below:-

Ethylenediamine can easily replace H2O from [Ni(H2O)6] as en is

a better ligand as compared to H2O, according to the
spectrochemical series. As we know en is a bidentate ligand
and thus 1 molecule of en replaces 2 molecules of H 2O. Now we
have the summery of the experiment:-
We know the Cu+2 complexes have d9 electronic
configurations and are hence more stable in a distorted
octahedral geometry. So, [Cu(H2O)6]+2 has axial bonds
longer than the equatorial bonds. This distortion persists
even when other ligands replace H2O. So, when we try
to replace H2O by bidentate ligands like en there lies is a
problem.
The number of ligands that bind to a metal ion can be
determined using thermal measurements. In our case,
we measured the amount of heat evolved as
incremental amount of en is added. Thus, we will try to
measure the heat evolved as a function of the ratio of
moles of en to the moles of Ni+2/Cu+2.
We also utilized computational chemistry in order to
support our findings from above part of the experiment.
By constructing a Z matrix for a given molecule, we
model it in 3-d space and ran various
simulations/calculations on it. In this experiment, we
created a Z matrix for both the starting molecules,
[Ni(H2O)6]+2 and [Cu(H2O)6]+2. We then performed the
geometry optimization for both these molecules.
Also, another way to experimentally study Jahn Teller
distortion could be is using UV-Vis spectroscopy. In UV-
VIS absorption spectroscopy, distortion causes splitting
 of bands in the spectrum due to a reduction in
symmetry (Oh to D4h). So we took the UV-Vis of all the
mono,bi and tri dentate ligand compounds of both
copper and nickel.

PROCEDURE: -
DAY-1: Reaction of [Ni(H2O)6]+2 with ethylenediamine:-
a. Take 500mL, 0.15M [Ni(H2O)6]+2 in the calorimeter. 50ml of
1.5M ethylenediamine was added to this while continuous
stirring.
b. Plot temperature v/s time for roughly 3 min. After that add
another 50ml of 1.5M ethylenediamine.
c. Repeat the steps a & b until there is no temperature change
on adding more ethylenediamine.
d. Finally record the UV Visible spectrum of the contents of the
calorimeter.
DAY-2: Computational study of [Ni(H2O)6]+2 and
[Cu(H2O)6]+2 complexes:-
a. Create the Z matrix as well as the Cartesian coordinates for
the molecule by taking approximate values for the bond
distances and bond angles.
b. Feed the input file into Q-chem and perform geometry
optimization using LANL2DZ basis set.
c. Observe the trends for the optimized values of bond lengths
for both the complexes and site differences, if any.
DAY-3: Reaction of [Cu(H2O)6]+2 with ethylenediamine:-
Part-1: Synthesis of [Cu(H2O)6]+2:-
a. Prepare a 1M solution of CuSO4.5H2O in a 50 ml volumetric
flask.
b. Add conc. HCl to the solution prepared. The Solution should
turn green due to the formation of [CuCl4]-2.
c. Add some water to this green solution until it turns blue
again. This indicates the formation of [Cu(H2O)6]+2.
Part-2: Reaction of [Cu(H2O)6]+2 with ethylenediamine:-
a. Take 500mL, 0.15M [Cu(H2O)6]+2 in the calorimeter. 50ml of
1.5M ethylenediamine was added to this while continuous
stirring.
b. Plot temperature v/s time for roughly 3 min. After that add
another 50ml of 1.5M ethylenediamine.
c. Repeat the steps a & b until there is no temperature change
on adding more en. d. Finally record the UV Visible spectrum of
the contents of the calorimeter.

Results and Discussion:-

Show Jahn Teller effect using calorimeter method:-
H total for reaction of Ni[(H20)6]+2 and [Cu(H2O)6]+2 with en.

This can be calculated as:-

H = (Heat)/Moles = [(specific heat of solution) x (total

grams solution) x ( T)]/moles.

Taking specific heat for the complexes as = 4.184 J/g

Density = 1.0g/ml.
Ni[(H20)6]+2:-
Ti Tf Dens Volu Ma c T H H (Kj/
ity me ss mol)
26. 26. 1 550 550 4.1 0.6 1449. 19330.0
32 95 84 3 756 8
29. 30. 1 600 600 4.1 1.0 2686. 35815.0
86 93 84 7 128 4
31. 32. 1 650 650 4.1 0.6 1631. 21756.8
6 2 84 76
32. 32. 1 700 700 4.1 0 0 0
33 33 84
[Cu(H2O)6]+2:-
Ti Tf Dens Volu Ma c T H H (Kj/
ity me ss mol)
25. 28. 1 550 550 4.1 2.7 6397. 85297.8
95 73 84 8 336 1
36. 40. 1 600 600 4.1 3.5 8836. 117821.
94 46 84 2 608 4
42. 42. 1 650 650 4.1 0 0 0
41 41 84

Discussion:-
For the case of Ni, it will be observed that the amount of heat
evolved increases as we increase the ratio of en: Ni from 1:1 to
2:1 to 3:1 but remains fairly constant after that. This confirms
that three en molecules coordinate with one Ni +2. This confirms
that three en molecules coordinate with one Ni +2.
But in case of Cu, due to some experimental error we
cannot conclude but theoretically but we have that [Cu(H 2O)6]+2
has axial bonds longer than the equatorial bonds. This
distortion persists even when other ligands replace H 2O. So,
when we try to replace H2O by bidentate ligands like en there is
a problem. The distance between the 2 N atoms of en is
constant as the length of carbon backbone must remain
constant. So, we cannot be sure whether the en ligand can
completely span the octahedron. Thus the number of en ligands
that bind with Cu+2 must be lesser than 3.
Geometry optimization using LANL2DZ basis set :-
[Ni(H2O)6]+2 :-
 [Cu(H2O)6]+2:-
 Ni(en)3 :-
 Cu(en)2(H2O)2:-
Discussion:-
Now we have in this the optimized geometry, we are able to
see that the lengths of axial bonds will be elongated as
compared to the equatorial bonds in case of Cu. However in
case of Ni complex, no such distortion is observed.
We also find out that in case of Cu Jahn Teller Effect is
prominent therefore we have the compound formed as
Cu(en)2(H2O)2 on optimization. Whereas in Ni(en)3 we have all
the Ni-N bonds of the same length.
Jahn Teller distortion using UV-Vis spectroscopy:-

Cu Compounds:-
INTENSITY Vs WAVELENGTH Graph:-
2.5

Absorbance [A.U]
1.5
2en
3en
1 cucl
hexahydrate

0.5

0
200 250 300 350 400 450 500 550 600

Ni Compounds:-

UV Vis Spectra
0.1

0.08

0.06 nicl2
soln1
Absorbance 0.04
soln2
0.02 soln3

0
300 350 400 450 500
-0.02

Wavelength (nm)
Discussion :-
In this as we can see that the UV Vis spectra shows that the
compounds NiCl2 shows peak around 390 nm and as for mono,
bi and tri dentate ones too have peaks which corresponds to
the colour of the compound. In this we have that the 2en and
3en will have no change in color as due to Jahn Teller effect 2
en group can at maximum attach with the [Cu(H 2O)6]+2.

CONCLUSION:-
We used three different methods of thermal measurement,
geometric optimization using LANL2DZ basis set and the UV-
Vis Spectroscopy to finally come to conclusion that Cu 2+
complexes shows Jahn Teller effect and Ni2+ complex dont.

PRECAUTIONS:-
Sonicate the compound of [Ni(H2O)6]+2 and [Cu(H2O)6]+2
properly as they will not give proper results on doing
thermal measurements.
Handle concentrated HCl (12N) with care, pour it using a
funnel.
Keep the cuvette clean for good uv-vis data.