Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes

Ong Zhy Hui

21572185 14th Feb 2017

Title: Experiment 2 Electronic Spectra of Copper (II) and Nickel (II) Complexes

Aims: To record the visible spectra of several copper (II) and nickel (II)
transition metal complexes. To
assign the observed bands on the basis of ligand field theory. To calculate the
extinction
coefficient of each band and compare them with the expected values derived
from quantum
mechanical selection rules. To study the spectral effects of changing ligands
bonded to a metal
ion and to establish a spectrochemical series that reflects an increasing ligand
field.

Abstract:

Part A: The Copper (II) Complex, [Cu(en)2(H2O)2]I2 is synthesized. The weight

and the percentage of yield
of the product are recorded and calculated. Another 3 Copper (II) Complexes:
[Cu(H2O)6]2+,
[Cu(EDTA)]2-, [Cu(en)2(H2O)2]2+ are also synthesized. The UV Spectra are
studied and recorded for
each of the three solutions for the range 400 900 nm calibrated against a
water blank. The
maximum wavelength (max), maximum absorbance, frequency (), molar
extinction coefficient ()
and the ligand field parameter (o) are identified. The spectrochemical series
for 3 of the Copper
(II) Complexes are also determined by looking at the o.

Part B: The Nickel (II) Complexes, [Ni(H2O)6]2+, [Ni(en)3]2+, [Ni(NH3)6]2+ are

synthesised. The colour of 3 Nickel (II) Complexes are observed. The UV
Spectra of the 4 complexes are measured and recorded: [Ni(H2O)6]2+,
[Ni(NH3)6]2+, [Ni(DMSO)6]2+ between 890 and 340 nm, and [Ni(en)3]2+ between
890 and 320 nm. The maximum wavelength (max), maximum absorbance,
frequency (), molar extinction coefficient () and the ligand field parameter
(o) are identified. The spectrochemical series for 4 of the Nickel (II)
Complexes are determined by looking at the o.

Methods:

Part A: Preparation of Diaquabis (ethylenediamine) Copper (II) Iodide:

[Cu(en)2(H2O)2]I2
Copper (II) acetate monohydrate (1.9 g) is mixed with water (5 ml) in a 100 ml
Erlenmeyer flask.
Ethylenediamine (2.0 ml, 1.8 g) is added dropwise with stirring. Potassium
iodide (4.2 g) is
dissolved in a minimum volume of water in a separate flask and the two
solutions are mixed. The
reaction mixture is heated to 60C on a water bath. Any undissolved material
Page | 1
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

is removed by
filtration of the hot solution through a fluted no.4 filter paper. The resulting
mixture is cooled to
room temperature. The filtrate is cooled in an ice bath for at least 10 mins to
allow precipitation
of the product. The crude product is collected by vacuum filtration on a
sintered crucible. The
crude compound is purified by recrystallization from a minimum volume of hot
water. The crude
compound is collected by filtration on a sintered crucible, then washed with
cold ethanol and air
dried by continuing to draw air through the filter crucible. The crude
compound is dried overnight
in a vacuum desiccator.

Preparation of Solutions
(i) [Cu(H2O)6]2+ (O6 donor set) Approximately 1.00 g of copper (II) sulfate
pentahydrate is dissolved in 100 ml of water.

(ii) [Cu(EDTA)]2- (N2O4 donor set) Approximately 0.15 g of copper (II) acetate
monohydrate and approximately 0.40 g of sodium
dihydrogenethylenediaminetetraacetate (Na2H2EDTA) are dissolved in 100 ml
of water.

(iii) [Cu(en)2(H2O)2]2+ (N4O2 donor set) Approximately 0.50 g of diaquabis

(ethylenediamine) copper (II) iodide is dissolved in 100 ml of water.

Part B: The Electronic Spectra of Nickel (II) Complexes

Preparation of Solutions
Approximately 16 ml of aqueous 0.05 M Ni(NO3)2 solution is obtained and
divided into 5 ml
portions in three small conical flasks. 5 ml of concentrated ammonia is added
to the first flask
and 5 ml of ethylenediamine (NH2CH2CH2NH2) to the second flask in a fume
hood. The solutions
are mixed by shaking the flasks and visually compared the colours of the
resulting solutions with
that of the original solution in the 3rd flask. 5 ml of H2O is added to a 5 ml
portion of the aqueous
0.05 M Ni(NO3)2 solution.

Results:

Part A: Preparation of [Cu(en)2(H2O)2]I2

Formula weight of Cu(II)(OAc)2.H2O = 199.65 g mol-1

Weight of Cu(II)(OAc)2.H2O = 1.900 g
Moles of Cu(II)(OAc)2.H2O = 0.00952 mols

Page | 2
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

Formula weight of product [Cu(en)2(H2O)2]I2 = 63.546 + 2(60.100) +

2(18.015) + 2(126.904)
473.58 g mol-1

Weight of crude product = 3.963 g

Moles of crude product = 0.00837 mols

Equation for reaction: (CHCO2)CuHO + 2NHCHCHNH + 2KI + HO

[Cu(NHCHCHNH)(HO)]I + 2CHCOOK

0.00837
% yield of [Cu(en)2(H2O)2]I2 Crude =
100
0.00952

= 87.92%

Calculations

i. Determine the values of max for each complex.

Table 1: Maximum wavelengths of Cu(II) Complexes

Complex max (nm)

[Cu(H2O)6]2+ 812.00
2-
[Cu(EDTA)] 733.50
2+
[Cu(en)2(H2O)2] 547.50

ii. A = l[c]
A
= l[c ]

Table 2: Concentrations of Cu(II) Complexes

Formula
Mass Volum Concentrati
Compound Mass (g Moles
(g) e (L) on (M)
mol-1)
1.000 4.005 x 103
249.685 0.1000
CuSO4.5H2O 249.685 1.000 0.1000
= 4.005 = 4.005 x 10-
x 10-3 2

Cu(CO2CH3)2. 199.650 0.150 0.150 0.1000 7.513 x 104

H2O 199.650 0.1000
= 7.513 = 7.513 x 10-
Page | 3
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

x 10-4 3

0.500 1.056 x 103

[Cu(en)2. 473.58 0.1000
473.58 0.500 0.1000
(H2O)2]I2 = 1.056 = 1.056 x 10-
x 10-3 2

Table 3: Molar Extinction Coefficient of Cu(II) Complexes

Molar Extinction
Concentrat max Absorba
Compound Coefficient ()
ion (M) (nm) nce
(M-1cm-1)
0.490
1 (4.005 102)
CuSO4.5H2O 4.005 x 10-2 812.00 0.490
=
12.235
0.666
Cu(CO2CH3)2. 1 (7.513 103 )
7.513 x 10-3 733.50 0.666
H2O
=
88.646
0.660
2
[Cu(en)2. 1 (1.056 10 )
1.056 x 10-2 547.50 0.660
(H2O)2]I2
=
62.500

1
iii. E = = ( nm) (1 x 107) cm-1

Table 4: Frequencies of Cu(II) Complexes

Complex max (nm) (cm-1)

107
812.00 =
[Cu(H2O)6]2+ 812.00
12315.27
7
10
733.50 =
[Cu(EDTA)]2- 733.50
13633.27

Page | 4
 Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

107
547.50 =
[Cu(en)2(H2O)2]2+ 547.50
18624.84

h c
iv. o =

Table 5: Ligand field parameters of Cu(II) Complexes

Complex max (nm) o

34 8
(6.626 10 )(3.00 10 )
[Cu(H2O)6]2+ 812.00 812.00

= 2.448 x 10-28
(6.626 1034 )(3.00 10 8)
[Cu(EDTA)]2- 733.50 733.50

= 2.710 x 10-28
34 8
(6.626 10 )(3.00 10 )
[Cu(en)2(H2O)2]2+ 547.50 547.50

= 3.631 x 10-28

Table 6: Summary of Spectral Data

(cm-
Complex max (nm) max (cm-1) 1 o
Lmol-1)
2.448 x
[Cu(H2O)6]2+ 812.00 12315.27 12.235
10-28
2.710 x
[Cu(EDTA)]2- 733.50 13633.27 88.646
10-28
[Cu(en)2(H2O)2]2 3.631 x
+ 547.50 18624.84 62.500
10-28

Part B: The Electronic Spectra of Nickel (II) Complexes

Calculations

i. Range of visible wavelength: 400 to 800 nm

Table 7: Maximum absorbance and maximum wavelengths of Ni(II) Complexes

Complex Absorbance max (nm)

[Ni(H2O)6]2+ 0.043 722.50
[Ni(en)3] 2+
0.189 543.00 Page | 5
[Ni(NH3)6]2+ 0.115 572.00
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

ii. Table 8: Concentrations of Ni(II) Complexes

Initial Initial Final Final

Compound Volume Concentration Volume Concentration
(L) of Ni(NO3)2 (M) (L) of Ni(NO3)2 (M)
0.05 0.05
0.10 =
[Ni(H2O)6]2+ 0.05 0.05 0.10
0.025
0.05 0.05
0.10 =
[Ni(en)3]2+ 0.05 0.05 0.10
0.025
0.05 0.05
0.10 =
[Ni(NH3)6]2+ 0.05 0.05 0.10
0.025

Table 9: Molar extinction coefficients of Ni(II) Complexes

Molar Extinction
Concentra max Absorban
Compound Coefficient () (M-
tion (M) (nm) ce 1
cm-1)
0.043
1 (0.025) =
[Ni(H2O)6]2+ 0.025 722.50 0.043
1.72
0.189
1 (0.025) =
[Ni(en)3]2+ 0.025 543.00 0.189
7.56
0.115
1 (0.025) =
[Ni(NH3)6]2+ 0.025 572.00 0.115
4.60

Page | 6
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

iii., iv. Table 10: Summary of Spectral Data

1
E = = ( nm) (1 x 107) cm-1

2 3
Complex Absorban (M- Absorban (M-
nm 1 nm
ce cm-1) ce 1
cm-1)
0.043 0.035
722. 1 (0.025) 657.5 1 (0.025)
[Ni(H2O)6]2+ 0.043 0.035
50 0
= 1.72 = 1.40
0.047 0.115
797. 1 (0.025) 572.0 1 (0.025)
[Ni(NH3)6]2+ 0.047 0.115
50 0
= 1.88 = 4.60
0.161 0.189
806. 1 (0.025) 543.0 1 (0.025)
[Ni(en)3]2+ 0.161 0.189
50 0
= 6.44 = 7.56

Table 11: Summary of Spectral Data

1 2 3
Complex
nm cm-1 nm cm-1 nm cm-1
7 7
10 10
107
722.50 657.50
1165.0 1165.00 722. 657.
[Ni(H2O)6]2+ 1.72 1.40
0 50 = 50 =
=
13840.8 15209.1
8583.69
3 3
107
[Ni(DMSO)6] 1290.0 1290.00
2+
0
=
7751.94

Page | 7
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

107 107 107

943.00 797.50 572.00
797. 572.
[Ni(NH3)6]2+ 943.00 1.88 4.60
= 50 = 00 =
10604.4 12539.1 17482.5
5 8 2
107 107 107
875.00 806.50 543.00
806. 543.
[Ni(en)3]2+ 875.00 6.44 7.56
= 50 = 00 =
11428.5 12399.2 18416.2
7 6 1

v. Table 12: Calculated Ligand Field Parameters

h c
o =

Complex max (nm) o

34 8
(6.626 10 )(3.00 10 ) 28
[Ni(H2O)6]2+ 722.50 =2.751 10
722.50
34 8
(6.626 10 )(3.00 10 )
[Ni(DMSO)6] 2+
1290.00 =1.541 1028
1290.00
34 8
(6.626 10 )(3.00 10 ) 28
[Ni(NH3)6] 2+
572.00 =3.475 10
572.00

(6.626 1034 )(3.00 10 8)

[Ni(en)3]2+ 543.00 =3.661 1028
543.00

vi. [Ni(DMSO)6]2+ < [Ni(H2O)6]2+ < [Ni(NH3)6]2+ < [Ni(en)3]2+

The spectrochemical series of ligands are as above in term of increasing of o
from the left to
right.
No. It does not different from the expected spectrochemical series. (As shown
below)
DMSO < H2O < NH3 < en

Discussion:

Part A: The Electronic Spectra of Copper (II) Complexes

1) Yes. The values of o obtained support the trend predicted from the
spectrochemical series.
The spectrochemical series obtained from the experiment is [Cu(H2O)6]2+ <
Page | 8
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

[Cu(EDTA)]2- <
[Cu(en)2(H2O)2]2+ with o increasing from the left to right. Whereas the
predicted
spectrochemical series is H2O < EDTA < en.

2) I predict that the value of o for [Cu(en)3]2+ will be higher than that of
[Cu(en)2(H2O)2]2+
(i.e. o > 3.631 x 10-28).

3) Yes. The molar extinction coefficients are consistent with d-d electronic
transitions. The molar
extinction coefficients of the 3 Cu complexes are [Cu(H2O)6]2+ - 12.235 M-
1
cm-1, [Cu(EDTA)]2- -
88.646 M-1cm-1 and [Cu(en)2(H2O)2]2+ - 62.500 M-1cm-1 where 3 of them lie in
the range of 1
102 M-1cm-1 which the d-d bands of 6-coordinate complexes in general and
of some square
planar complexes.

4)

5) Tetragonal distortion is also known as Jahn-Teller Distortions which is

commonly observed for
Cu (II) complexes because it usually occurred in octahedral complexes of
the transition metals.
The d9 electronic configuration of this ion gives 3 electrons in the 2
degenerate eg orbitals,
leading to a doubly degenerate electronic ground state. Such complexes
distort along one of
the molecular fourfold axes (z axis), which has the effect of removing the
orbital and electronic
degeneracies and lowering the overall energy.

6) Optical isomerism

Page | 9
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

Part B: The Electronic Spectra of Nickel (II) Complexes

1) In this experiment, the obtained colours for [Ni(H2O)6]2+ is green,

[Ni(NH3)6]2+ is purple and
[Ni(en)3]2+ is pink. This is consistent with what we expect from the max,
where max of
[Ni(H2O)6]2+ is 722.50 nm which absorbed red colour and transmitted green
colour. max of
[Ni(NH3)6]2+ is 572.00 nm which absorbed yellow colour and transmitted
violet colour. max of
[Ni(en)3]2+ is 543.00 nm which absorbed green colour and transmitted red
colour.

2) [Co(H2O)6]2+ < [Co(NH3)6]2+ ; [Co(H2O)6]2+ absorbs at a longer wavelength.

[Co(NH3)6]2+ < [Co(NH3)6]3+ ; [Co(NH3)6]2+ absorbs at a longer wavelength.

[Co(NH3)6]3+ < [Rh(NH3)6]3+ ; [Co(NH3)6]2+ absorbs at a longer wavelength.
[FeF6]3- < [Fe(CN)6]3- ; [FeF6]3- absorbs at a longer wavelength.
h c
This is can be explained by referring to this formula o = , this

showed that the larger the ,

the smaller the o.

Conclusions:

Part A: The percentage yield obtained for the crude product [Cu(en)2(H2O)2]I2 is
87.92%. The summary of
the Copper (II) Complexes Spectral Data is tabulated in Table 6. Based on the
results, the
spectrochemical series of Cu(II) Complexes is [Cu(H2O)6]2+ < [Cu(EDTA)]2- <
[Cu(en)2(H2O)2]2+ which
are in terms of increasing of the ligand field parameter o.

Part B: The summary of the Nickel (II) Complexes Spectral Data is tabulated in
Table 11 and the
calculated ligand field parameters are in Table 12. Based on the results, the
Page | 10
Experiment 2: Electronic Spectra of Copper (II) and Nickel (II) Complexes
Ong Zhy Hui
21572185 14th Feb 2017

spectrochemical
series of Ni(II) Complexes is [Ni(DMSO)6]2+ < [Ni(H2O)6]2+ < [Ni(NH3)6]2+ <
[Ni(en)3]2+ which are in
terms of increasing of the ligand field parameter o. The colours of the 3 Ni(II)
Complexes are
determined and verified with the maximum wavelengths. [Ni(H2O)6]2+ showed
green colour,
[Ni(NH3)6]2+ showed purple colour and [Ni(en)3]2+ is pink colour.

References:

1. D.F. Shriver, P.W. Atkins: Inorganic Chemistry, 2 nd Edn., 1994, Chapters 6 & 14.
3rd Ed Chapters 7 and 13.

2. Tomohiko Ishii, Shino Tsuboi, Genta Sakane, Masahiro Yamashita and Brian K.
Breedlove: Universal Spectrochemical Series of six-coordinate Octahedral Metal
Complexes for Modifying the Ligand Splitting, Dalton Transactions, 2009, pp 680-
687.

3. Janes, Rob; Moore, Elaine A. (2004). Metal-ligand bonding. Royal Society of

Chemistry.

4. Thomas J. Bruno, Paris D. N. Svoronos. CRC Handbook of Fundamental

Spectroscopic Correlation Charts

Page | 11