Introduction
The coordination geometries of nickel(II) complexes are extremely sensitive to changes in the
ligand set. For example, a number of complexes of the type [Ni(PR 3)2X2] exhibit a square planar
to tetrahedral equilibrium in solution, a result of the very small energy difference between the two
geometries. The geometry adopted depends on both electronic and steric effects. A more bulky
phosphine ligand (e.g. tricyclohexylphosphine) will shift the equilibrium towards the tetrahedral
form, whilst decreasing the bulk makes the square planar form more accessible. Similarly,
stronger field ligands increase the tendency to a square planar geometry.
PR3
R3P X
Ni
Ni
X R3P X
R3P
X
Experimental
a) Preparation of Dichlorobis(triphenylphosphine)nickel(II)
- Dissolve nickel chloride hexahydrate (1.2 g) in dry ethanol (15 cm 3) and warm gently.
- Place triphenylphosphine (2.8 g) and isopropanol (30 cm 3) in a 100 cm 3 round-bottomed flask,
fit a reflux condenser and dissolve the phosphine by refluxing gently.
- When the phosphine has dissolved, remove from the heat and carefully add the warm nickel
chloride solution.
- Reflux the mixture for a further 10 minutes and then cool to room temperature.
- Filter the product in a Buchner flask, wash with cold ethanol (15 cm 3 ) followed by diethyl ether
(15 cm3) and draw a stream of air through the product to dry.
- Record the yield (g , %).
d) Investigation
Questions
1. Calculate the effective magnetic moments of each of your compounds. What geometries
do these results suggest for each of the compounds?
2. Compare your UV-visible spectra. Do these support your conclusions on the basis of
your magnetic measurements?
3. Thiocyanate is an ambidentate ligand. From your infra-red spectrum deduce how it is
bound to the nickel centre.
4. Rationalise your results in terms of the donor properties of the ligands.
5. Using your results from the crystallographic database, correlate the structures adopted
(square planar or tetrahedral) with the type of halide and both the steric bulk and electron
donor ability of the phosphines.