Liquid ammonia metathesis reactions

In order for a metathesis reaction to occur in water, some product must be removed from the reaction. Generally, this involves the formation of a precipitate, the evolution of a gas, or the formation of an unionized product. Because solubilities are different in liquid ammonia, reactions are often unlike those in water. Although silver halides are insoluble in water, they are soluble in liquid ammonia as a result of forming stable complexes with ammonia. Therefore, the reaction... 

The first of these reactions takes place because AgCl is insoluble in water. The second takes place because AgCl is insoluble in sulfur dioxide. The third reaction takes place because the highly ionic LiCl is not soluble in liquid ammonia. The last of these reactions takes place because AgCl is soluble in liquid ammonia but NaCl is not. It is clear that metathesis reactions may be different in some nonaqueous solvents. 

The small steric size and propensity of cyanide groups to bridge metal centers have limited their use as ligands in molecular coordination chemistry of the actinides, where they are prone to form amorphous polymeric products. Limited metathesis studies have been conducted. Reaction of tetravalent halides with alkali metal cyanides in liquid ammonia is reported to give rise to a product of the formula UX3(CN)-4NH3, whereas use of the larger thorium ion yields unidentified products. 

In fact, however, some triester (ro)2P(S)-SR and probably some polymeric product is also formed. In careful synthetic work, the esterification is carried out by slowly adding the theoretical amount of P S q to the hydroxylic compound ROH. If the hydroxylic reactant is a liquid, it acts as its own solvent for the reaction otherwise an appropriate inert solvent is used. In preparing pure phosphorodithioic esters, useful intermediates are the ammonium salts, which are well defined solids formed by the action of dry gaseous ammonia on the crude initial esterification product. These salts can be purified by recrystallization from a solvent such as benzene. The metallic salt is prepared by metathesis in aqueous solution at carefully controlled pH for example ... 

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