THE KINETICS OF THE THALLIUM(III) ION-PROMOTED HYDROLYSIS OF DITHIOURETHANES

In aqueous acid in the presence of Tl3+ ions the N-aryl S-aryl dithiou rethanes (dithiocarbamates) 2 and 3 rapidly form complexes of 1:1 dith iourethane:Tl3+ stoichiometry which decompose to the corresponding iso thiocyanates; this elimination is accelerated by an excess of Tl3+ ion s in a process first order in Tl3+! with DELTAS(double dagger) almost -equal-to -100 J K-1 mol-1 and in which compound 3 is ca. three-fold m ore reactive than 2.