INVESTIGADORES
URANGA Jorge Gustavo
artículos
Título:
Inter- and Intramolecular-Bridge-Mediated Electron Transfer in Aliphatic Halides
Autor/es:
URANGA J. G., VERA, D.M.A., SANTIAGO,A.N. AND PIERINI A.B.
Revista:
JOURNAL OF ORGANIC CHEMISTRY
Editorial:
AMER CHEMICAL SOC
Referencias:
Año: 2006 vol. 71 p. 6596 - 6599
ISSN:
0022-3263
Resumen:
The anionic surfaces of the 1-chloro- and 4-chlorobicyclo-
[2.2.1]heptan-2-one, 1-chloro- and 4-chlorobicyclo[2.2.2]-
octan-2-one, 1-chloro- and 5-chloroadamantan-2-one, and
2-chlorotricyclo[7.3.1.02,7]tridecan-13-one were explored
using DFT functionals with full geometry optimization in
solution. The reductive cleavage of these compounds is
controlled by the rigidity of the polycycle, its capability to
form an unstrained radical, and by the relative carbonyl/CCl
disposition on the bridge. Such control can be exerted by
either a concerted-dissociative or a stepwise mechanism with
radical anions as intermediates. 5-Chloroadamantan-2-one
is the most suitable compound to follow the latter pathway.
using DFT functionals with full geometry optimization in
solution. The reductive cleavage of these compounds is
controlled by the rigidity of the polycycle, its capability to
form an unstrained radical, and by the relative carbonyl/CCl
disposition on the bridge. Such control can be exerted by
either a concerted-dissociative or a stepwise mechanism with
radical anions as intermediates. 5-Chloroadamantan-2-one
is the most suitable compound to follow the latter pathway.
2,7]tridecan-13-one were explored
using DFT functionals with full geometry optimization in
solution. The reductive cleavage of these compounds is
controlled by the rigidity of the polycycle, its capability to
form an unstrained radical, and by the relative carbonyl/CCl
disposition on the bridge. Such control can be exerted by
either a concerted-dissociative or a stepwise mechanism with
radical anions as intermediates. 5-Chloroadamantan-2-one
is the most suitable compound to follow the latter pathway.