Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

Moreira, José; García-Río, Luís; Leis, J. R.; Adam, C.

http://hdl.handle.net/10400.1/3225

Use this identifier to reference this record.

Name:	Description:	Size:	Format:
Tetrahedron 2006 Adam.pdf		367.57 KB	Adobe PDF	Download

Send Feedback

Authors

Abstract(s)

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)(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.

Keywords

Kinetics Mechanism Nitrosation Thiol Sulfonamide

URI

http://hdl.handle.net/10400.1/3225

Citation

Moreira, 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.