The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (αlg≈− 1.30), but virtually independent of the basicity of the thiol (βnuc≈ 0.10). This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (βd) that is followed by the attack of the thiolate ion on the nitroso group (βnuc′) via a concerted ...
