C. Andrieux, E. Differding, M. Robert
Jul 1, 1993
Citations
0
Influential Citations
54
Citations
Journal
Journal of the American Chemical Society
Abstract
The cyclic voltammetry of the reductive cleavage of N-fluoro-, N-chloro-, and N-bromosaccharin sultams and of their 4-nitro-substituted analogues was investigated in acetonitrile at an inert electrode. The seriin of compounds provides particularly clear evidence that the two main factors governing the occurrence of a stepwise or a concerted mechanism in reductive cleavages are the energy of the π * orbital, possibly accommodating the incoming electron, and the strength of the breaking bond. In the concerted cases, application of the theory of dissociative electron transfer allowed the intimation of the nitrogen-halogen bond dissociation energy and of the standard potential and intrinsic barrier of the reaction