Moreira, JoséGarcía-Río, LuísLeis, J. R.Adam, C.2013-12-062013-12-062006Moreira, José A.; García-Río, Luís; Ramón Leis, José; Adam, Cláudia. Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity, Tetrahedron, 62, 37, 8822-8829, 2006.0040-4020AUT: JMO01545;http://hdl.handle.net/10400.1/3225The 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)(αlg≈−1.30), but virtually independent of the basicity of the thiol (βnuc≈0.10)(βnuc≈0.10). This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (βd)(βd) that is followed by the attack of the thiolate ion on the nitroso group (βnuc′) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonamide were used to obtain the equilibrium constants for the different reactions involved. By using rate–equilibrium correlations, the parameters αlgnorm, βdβd, and βnuc′norm were obtained.engKineticsMechanismNitrosationThiolSulfonamidejournal article2013-12-04http://dx.doi.org/10.1016/j.tet.2006.06.060