Sulfur compounds in free radical reactions. Part II: Thermal decomposition of arenediazothiolates

Arenediazothiolates (Ar‐NN‐SR; R  alkyl or aryl) undergo homolysis on heating. This follows from substituent and solvent effects on decomposition rates; product formation is interpretable on a homolytic basis. Substituent as well as solvent viscosity effects suggest that the primary step consists in the formation of a radical pair {article}{empty}{document}\[({Ar-{ N}_2^•+{ RS}^•})\]{document} rather than multiple fission {article}{empty}{document}\[({Ar-{ N}_2^•+{ RS}^•})\]{document} . In contrast to the situation at high concentration hardly any induced decomposition takes place at the low concentrations used for kinetics.