Cerium(III) chloride (CeCl<sub>3</sub>), also known as cerous chloride or cerium trichloride, is a compound of cerium and chlorine. It is a white hygroscopic salt; it rapidly absorbs water to form hydrates, which may be of variable composition.The hexa- and heptahydrate CeCl<sub>3</sub>÷7H<sub>2</sub>O are known. All forms are highly soluble in water, and the anhydrous derivative is soluble in ethanol and acetone.
Simple rapid heating of the hydrate alone may cause small amounts of hydrolysis.
A useful form of anhydrous CeCl<sub>3</sub> can be prepared if care is taken to heat the heptahydrate gradually to over many hours under vacuum. This may or may not contain a little CeOCl from hydrolysis, but it is suitable for use with organolithium and Grignard reagents. Pure anhydrous CeCl<sub>3</sub> can be made by dehydration of the hydrate either by slowly heating to with 4âÂÂ6 equivalents of ammonium chloride under high vacuum, or by heating with an excess of thionyl chloride for three hours. The anhydrous halide may alternatively be prepared from cerium metal and hydrogen chloride. It is usually purified by high temperature sublimation under high vacuum. Soxhlet extraction of with thf gives .
Cerium(III) chloride can be used as a starting point for the preparation of other cerium salts, such as the Lewis acid cerium(III) trifluoromethanesulfonate.
Cerium(III) chloride is a reagent in several procedures used in organic synthesis. Luche reduction of alpha, beta-unsaturated carbonyl compounds has become a popular method in organic synthesis, where CeCl<sub>3</sub>÷7H<sub>2</sub>O is used in conjunction with sodium borohydride. For example, carvone gives only the allylic alcohol 1 and none of the saturated alcohol 2. Without CeCl<sub>3</sub>, a mixture of 1 and 2 is formed.
It can also deprotect MEM group to alcohol in the presence of other acetal protecting groups (e.g. THP.)
Another important use in organic synthesis is for alkylation of ketones, which would otherwise form enolates if simple organolithium reagents were to be used. For example, compound 3 would be expected to simply form an enolate without CeCl<sub>3</sub> being present, but in the presence of CeCl<sub>3</sub> smooth alkylation occurs:
It is reported that organolithium reagents work more effectively in this reaction than do Grignard reagents.