Kinetics of the Mercury(II) Ion-promoted Desulfurisation of Thiocarbamates in Aqueous Solution

Article abstract of DOI:10.1039/P29920001091

In a 1percent dioxane-water solvent in the presence of Hg²⁺ ions thiocarbamates p-RC6H4NHC(S)OEt (R = MeO, Me, H, F) rapidly form complexes of 2 thiocarbamate: 1 Hg²⁺ stoichiometry.In the presence of an excess of Hg²⁺ ions partial conversion to the 2:2-complexes probably occurs which decompose to the corresponding carbamates (p-RC6H4NHCO2Et) and HgS.With R = NO2 the 2:2 complex is dominant even at low Hg²⁺ ion concentrations, and desulfurisation is then independent of 2+>.Electron-withdrawal by R favours the 2:2 complex but decreases its rate of decomposition to products.The effects of changes in the hydrogen ion concentration suggest that ionisation of N-bound protons in the complexes favours reaction.A mechanism is suggested.The kinetic behaviour is somewhat similar to that found previously for thiobenzamides, but the new results suggest the mechanism previously proposed may need revision.

Full text of DOI:10.1039/P29920001091

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