CHM-304

Determination of spectrochemical order of ligands by using

electronic spectroscopy of Nickel(II) coordination complexes
V N V AMAN DEEP
(18147)
May 13, 2022

Aim:
Determination of spectrochemical order of ligands by using electronic spectroscopy of Nickel(II) coordination complexes

Chemicals:
NiCl2 .6H2 O, ethylenediamine, methanol, acetone, ethanol, concentrated NH4 OH.

Glassware:
Beaker (100 mL x 2), (50 mL x 2), (25 mL x1), measuring cylinder (10 mL 50 mL), ice bath, dropper, glassrod, Buchner
funnel, filtration flask, conical flask (100 mL x 2), magnetic bar, spatula, graduated pipette, glass funnel, test tubes, test tube
stand, G4 crucible, sample vial (3 Nos.), volumetric flask (10 mL x 3 ), gloves.

Theory:
Coordination compounds are among the most extensively investigated molecules/areas in the field of inorganic chemistry; and
in fact, the first inorganic chemist to win a Nobel Prize (1913), Alfred Werner, for work on coordination compounds. These
compounds exhibit extensive and interesting spectral and magnetic properties in addition to widely varying structures and
stoichiometries. Coordination complexes have at least one metal complex, which contains a metal center and is surrounded
by electron- donating ligands. These ligands do not form ionic or covalent bonds with the metal center, rather they take on a
third type of bond known as coordinate bond.

Ligands are classified by the number of bonds, or attachments, they can make with a metal center. A single attachment
is known as monodentate (one-toothed). A ligand that makes two attachments is called bidentate (two-toothed), and three at-
tachments is known as tridentate. Ligands may be charged or neutral. Ligands are classified as being strong or weak according
to the spectrochemical series. When six ligands approach a metal center to form an octahedral complex, the five-degenerate
d-orbitals split into three lower-energy degenerate t2 g orbitals and two higher-energy degenerate eg orbitals. The distance of
the splitting between the t2 g and eg orbitals is dictated by the strength of the ligand according to the spectrochemical series.

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 In this experiment we will prepare coordination complexes of nickel and determine the spectrochemical ordering of several
ligands using UV-Visible spectroscopy. Because the distance in orbital splitting varies with ligand strength, a coordination
complex with the same metal center can have a variety of colors based upon the coordinating ligand. The color arises from
the change in energy between the t2 g-eg orbitals.

Procedure:
The preparation of [Ni(en)3 ]Cl2 .2H2 O.
1. 6.0 g of NiCl2 .6H2 O was dissovled in 3 mL of H2 O in a 100 mL beaker. A little warming improved the rate of
dissolution.
2. The ethylenediamine was added slowly because the reaction was quite exothermic. The reaction mixture was cooled.
10 mL of cold ethanol was added to initiate crystallization.It was kept in cold environment for 10 min.
3. The product was colleted on a Büchner funnel and washed with 3 mL portions of ethanol. Dry in air and recorded the
yield.

The preparation of [Ni(NH3 )6 ]Cl2

3.0 g of NiCl2 .6H2 O was dislved in 5 mL of warm H2 O in a 100 mL Erlenmeyer flask and 5.8 mL of concentrated NH4 OH
was added and cooled with an ice bath and observed the precipitation of large violet crystals. 10 mL of cold ethanol was added
to complete the precipitation. The crystals on a Büchner funnel was collected and washed with 3 mL portions of ethanol. Dry
in air and recorded the yield.

The preparation of [Ni(en)2 ]Cl2 .2H2 O

1. 1.25 g of NiCl2 .6H2 O and 3.02 g of [Ni(en)3 ]Cl2 .2H2 O were gently warmed( in 100 mL beaker on Mag. Stirrer) in a
mixture of 22 mL of methanol and 1.0 mL of H2O for 5 minutes.
2. The solution was kept hot and gravity filtered into a 100 mL conical. The flask was rinsed twice with 1.5 mL of hot
methanol. In order to initiate crystallization, The blue solution was cooled on ice.
3. The bulk-chilled solution was stirred and 25-30 mL of acetone was added drop wise for about two minutes. we continued
to stir for about 10 min after the last acetone addition. The blue crystals were colllected using a sintered glass filter.
Washed twice with 5-10 mL of acetone and allow to dry and recorded the yield.

observation
NiCl2 .6H2 O is green in colour.
[Ni(en)3 ]Cl2 .2H2 O is purple in colour.
[Ni(NH3 )6 ]Cl2 is violet in colour.
[Ni(en)2 ]Cl2 .2H2 O is blue in colour.

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Calculation
1. For preparation of [Ni(en)3 ]Cl2 .2H2 O(MW is 327.91), we were taking 6g of NiCl2 .6H2 O(MW is 237) i.e. 25.5mmol.
So theoretical yield is 25.5mmol× 327.91 = 8.2g.
Experimental yield is 6.72g
6.72
% of yield = × 100 = 81.9%.
8.2
2. For preparation of [Ni(NH3 )6 ]Cl2 (MW is 231.78), we were taking 3g of NiCl2 .6H2 O(MW is 237) i.e.12.75mmol.
So theoretical yield is 12.75mmol× 231.78 = 2.95g.
Experimental yield is 2.45g
2.45
% of yield = ×100 = 83%
2.95
3. For preparation of [Ni(en)2 ]Cl2 .2H2 O(MW is 267.8), we were taking 1.25g of NiCl2 .6H2 O(MW is 237) i.e. 5.25mmol(Limiting
reagent) and 3.02g of [Ni(en)3 ]Cl2 .2H2 O(MW is 327.91) i.e. 9.20mmol.
So theoretical yield is 5.25mmol× 267.8 = 1.40g.
Experimental yield is 1.255g
1.25
% of yield = ×100 = 89.3%
1.40

Characterization:
For visible spectra prepare 10 mL solution (in volumetric flask) of each complex-
1. Hexaminenickel(II) chloride 0.1 M(0.23g) in 50% NH4 OH,
2. bis- and tris-ethylenediaminenickel(II) chloride 0.1 M(0.327g) in H2 O

3. Nickel(II) chloride hexahydrate 0.1 M(0.23g) in H2 O.

So for Hexaminenickel(II) chloride, first sharp absorbance peak comes at ∼380nm(∼ 26000cm–1 ), another broad peak comes
at ∼590nm(∼ 17000cm–1 ).
For [Ni(en)3 ]Cl2 .2H2 O, first peak comes at ∼375nm(∼ 26666cm–1 ) and another broad peak at ∼575nm(∼ 17400cm–1 ).
For [Ni(en)2 ]Cl2 .2H2 O, first peak comes at ∼390nm(∼ 26000cm–1 ) and another broad peak at ∼590nm(∼ 17000cm–1 ). For
NiCl2 .6H2 O , first peak comes at ∼400nm(∼ 25000cm–1 ) and two broad peak at ∼660nm(∼ 15000cm–1 ) and ∼710nm(∼
14000cm–1 ).

Discussion
1. So for a d8 system, A2g → T2g transition= Δ and A2g → T1g and A2g → T1g (P) are higher in wavelength.

2. So for Hexaminenickel(II) chloride, A2g → T2g transition = ∼ 26000cm–1 (So is the Δ) and A2g → T1g transition =
∼ 17000cm–1 .

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Figure 1

Figure 2