Experiment 1

Spectroscopic and
Magnetochemical Properties of
Ni(II) Complexes in Different
Geometries
 
 
 
 
 
Tetrahedral complex – [Ni(PPh3)2Cl2]
Prepare a solution of [Ni(PPh3)2Cl2] by dissolving ca. 20 mg in 10
mL of dry dichloromethane in a volumetric flask. It is very
important in this section to use DRY dichloromethane as
[Ni(PPh3)2Cl2] is moisture sensitive and thus using ordinary
dichloromethane makes the solution cloudy is a few seconds.
Prepare the solution quickly and keep it stoppered. Record the
UV-Visible spectrum of this solution between 450 and 1100 nm.

Square planar complex – [Ni(PPh3)2(CO)2]

Prepare a solution of [Ni(PPh3)2(CO)2] by dissolving ca. 12 mg in
100 mL of dichloromethane in a volumetric flask. Record the UV-
Visible spectrum of this solution between 350 and 1100 nm.

Octahedral complex – NiCl2 in water and aqueous ammonia

Prepare a solution of [Ni(H2O)6]Cl2 by dissolving 0.238 g (1 mmol)
of NiCl2.6H2O in 10 mL of water in a volumetric flask. Similarly,
prepare a solution of [Ni(NH3)6]Cl2 by dissolving 0.238 g (1 mmol)
of NiCl2.6H2O in 10 mL of aqueous ammonia in a volumetric flask.
Record the UV-Visible spectrum of each solution between 350 and
1100 nm.

Preparation of NiL2Cl2.2H2O
In a conical flask, dissolve 1.19 g (5 mmol) of NiCl2.6H2O in 30 mL
ethanol. To this solution, add 1.40 mL (1.16 g, 10 mmol) of N,N-
diethyl-ethylenediamine, swirl the mixture thoroughly and keep it
to stand. After a certain moment (ca. 10-20 minutes), you will
notice the formation of light blue crystals. Filter off these
crystals using a small Hirsch funnel, wash them with the minimum
quantity of ethanol (preferably using a Pasteur pipette), and dry
by suction. When the complex is dry, record the yield and the UV-
Visible spectrum of the complex between 350 and 1100 nm after
dissolving ca. 40 mg of the complex in 10 mL of methanol.

Preparation of NiL2(BF4)2
In a conical flask, dissolve 1.70 g (5 mmol) of Ni(BF4)2.6H2O in 30
mL ethanol. To this solution, add 1.40 mL (1.16 g, 10 mmol) of N,N-
diethyl-ethylenediamine, swirl the mixture thoroughly and keep it
to stand. An orange precipitate forms quickly. Filter it off, wash
it with the minimum quantity of ethanol (preferably using a
Pasteur pipette), and dry by suction. When the complex is dry,
record the yield and the UV-Visible spectrum of the complex
between 400 and 1100 nm after dissolving ca. 45 mg of the complex
in 10 mL of nitromethane.

Preparation of [Ni(acac)2(H2O)2]
In a conical flask, dissolve 1.188 g (5 mmol) of NiCl2.6H2O and 0.82
g (10 mmol) of sodium acetate in 10 mL water. In a separate flask,
dissolve 1.0 g (10 mmol) of pentane-2,4-dione in 5 mL ethanol and
add it to the first mixture, swirl the flask to ensure complete
mixing. Put the flask in ice. In a few minutes, the precipitation of a
pale green solid will start. If crystallization does not start,
scratch the inside of the flask with a glass rod to induce it. When
the crystallization is complete (in about 15 minutes), collect the
precipitate in a Hirsch funnel, wash it with ethanol (no more than
2 mL), ether (2×10 mL) and allow keep it to air-dry for at least 30
minutes. When it is completely dry, record the yield and the UV-
Visible spectrum of the complex between 450 and 1100 nm after
dissolving ca. 30 mg of the complex in 10 mL of acetone.
 
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