Cuprous Thiourea Complexes

Synthesis of Tri(thiourea)-cuprous sulphate: [Cutu3]2SO4⋅2H2O and Tri(thiourea)-cuprous chloride:

[Cutu3]Cl. Either or both may be synthesised and brought to Dept. of Chemistry as part of the SRP-
Project 01.

(1) [Cutu3]2SO4⋅2H2O

Dissolve 4 g. (52.6 mmol) of thiourea in 25 mL of hot water, and then cool the solution to room
temperature. Shake the solution well while adding small portions of a cold solution of 4 g. (16.1
mmol) of copper sulphate pentahydrate, CuSO4⋅5H2O, in 20 mL of water. Finally, cool thoroughly
in running water until the separated yellowish oil adheres to the wall of the containing flask. Decant
and reject the mother-liquid. Shake the oil vigorously with a solution of 2 g. of thiourea in 20 mL of
water, until crystallisation is complete. Filter and wash the crystals with a small volume of water.
Recrystallise the material from a 5% aqueous solution of thiourea containing 2 mL of 0.5 M
sulphuric acid per 100 mL of solution. During recrystallisation the temperature of the solution
should not be allowed to rise above 80°C. Yield of recrystallised product, ca. 4.5 g. Like those of
the sulphates of the alkali metals, crystals of the complex sulphates belong to the orthorhombic
system, but are so richly faceted that it is difficult to discern a simple crystal habit. Thiourea acts as
both a reducing agent as well as ligand in this synthesis. 1

(2) [Cutu3]Cl

Dissolve 2.5 g of thiourea in 12.5 mL of hot water. Add 0.5 g. of copper turnings (or powder) to the
solution and then 2.5 mL of concentrated hydrochloric acid. Heat on the boiling water-bath, while
the copper dissolves with libration of hydrogen. Filter while hot, and then allow the solution to cool
slowly as crystals separate. Filter and wash with acetone. Yield, 1.45 g. The white elongated
(pseudo-)crystals are opaque and have a porcelain-like appearance. In fact, they consist of oriented
aggregates of much smaller, transparent true crystals. When recrystallised from 5% aqueous
thiourea solution acidified with a small amount of hydrochloric acid, the complex chloride, is seen
as well-formed square (tetragonal) prisms terminated by a square pyramid.

Charaterization:

Measure X-ray powder diffraction patterns of the prepared compounds and compare with calculated
patterns. These will be handed out at Dept. of Chemistry during the course of Project 01.

Questions:

How do you expect thiourea to coordinate to the Cu+ ions in [Cutu3]2SO4⋅2H2O and [Cutu3]Cl?

Explain how thiourea works as a reducing agent.

1
W. G. Palmer, Experimental Inorganic Chemistry, Cambridge University Press, 1962, page 132