CHEM 232 – Inorganic Synthesis

Spring 2018-2019

Experiment no. 1
Synthesis and Spectroscopic Properties
of Ni(II) Complexes in Different Geometries

A. Octahedral complex – NiCl2 in water and aqueous ammonia

1. 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.
2. Prepare a solution of [Ni(NH3)6]Cl2 by dissolving 0.238 g (1 mmol) of NiCl2.6H2O in
10 mL of aqueous ammonia (12.5 %) in a volumetric flask.
3. Prepare a solution of [Ni(H2O)6]Cl2 by dissolving 0.238 g (1 mmol) of NiCl2.6H2O in 5
mL of water in a volumetric flask. Add to the mixture 5 mL of aqueous ammonia (25.0
%).
4. Record the UV-Visible spectrum of each solution between 190 and 1100 nm.

B. Preparation of NiL2Cl2.2H2O
1. Dissolve in a beaker 1.19 g (5 mmol) of NiCl2.6H2O in 30 mL absolute ethanol.
2. Add under magnetic stirring to the obtained solution 1.40 mL (1.16 g, 10 mmol) of
N,N-diethyl-ethylenediamine and keep the mixture under stirring for 30 minutes. Leave
the mixture at rest for 10 minutes.
3. Using a small Büchner funnel, filter the solution and wash the remaining with the
minimum volume of ethanol (preferably no more than 2 mL). Dry by suction for an
hour.
4. When the complex is dry, record the yield and the UV-Visible spectrum of the complex
between 190 and 1100 nm after dissolving ca. 40 mg of the complex in 10 mL of
methanol.

C. Preparation of NiL2(BF4)2
1. In a beaker, dissolve 1.70 g (5 mmol) of Ni(BF4)2.6H2O in 30 mL ethanol to which add
1.40 mL (1.16 g, 10 mmol) of N,N-diethyl-ethylenediamine under stirring for 2 minutes.
An orange precipitate forms quickly.
2. Filter the solution off, wash the remaining with the minimum volume of ethanol
(preferably no more than 2 mL), and dry by suction for one hour.
3. When the complex is dry, record the yield and the UV-Visible spectrum of the complex
between 190 and 1100 nm after dissolving ca. 45 mg of the complex in 10 mL of
nitromethane.

D. Preparation of [Ni(acac)2(H2O)2]
1. Under magnetic stirring, dissolve in a beaker 1.188 g (5 mmol) of NiCl2.6H2O and 0.82
g (10 mmol) of sodium acetate in 10 mL water.
2. In a separate flask, dissolve under magnetic stirring 1.026 mL (1.0 g; 10 mmol) of
pentane-2,4-dione in 5 mL ethanol, add it to the first mixture and keep it under stirring
for 10 minutes.
3. Put the flask in an ice bath and keep it for a minimum of 30 minutes. You will notice
the formation of pale green/blue crystals. If crystallization does not start, scratch the
inside of the flask with a glass rod to induce it.
4. Filter the precipitate using a Büchner funnel, wash it first with ethanol (no more than 1
mL) followed by ether (twice, each 5 mL) and keep it to air-dry for at least 20 minutes.
5. Record the yield and the UV-Visible spectrum of the complex between 190 and 1100
nm after dissolving ca. 60 mg of the complex in 10 mL of distilled water.