THEORETICAL-STUDY OF THE ELECTROREDUCTION OF HALOGENATED AROMATIC-COMPOUNDS .3. O-DIBROMOBENZENES, M-DIBROMOBENZENES AND P-DIBROMOBENZENES STUDIES BY AM1 AND PM3 METHODS
R. Andreoli et al., THEORETICAL-STUDY OF THE ELECTROREDUCTION OF HALOGENATED AROMATIC-COMPOUNDS .3. O-DIBROMOBENZENES, M-DIBROMOBENZENES AND P-DIBROMOBENZENES STUDIES BY AM1 AND PM3 METHODS, Journal of the Chemical Society. Faraday transactions, 90(21), 1994, pp. 3241-3244
Citations number
29
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
The electroreductive potential values of the o-, m- and p-dibromobenze
nes (DBBs) follow an unusual pattern in that, unlike the structurally
related dichlorobenzene (DCB) derivatives, these three isomers exhibit
a strong 'ortho effect' and are accompanied by a large difference in
the E1/2 values. Any interference with the mechanism of reduction on t
he part of the chemical environment can be safely ruled out, given the
consistency of the E1/2 values obtained in four different solvents. T
he use of theoretical indices calculated by the PM3 method enables the
experimental behaviour of the DBBs to be rationalised on the basis of
the electronic structure of the neutral isolated molecule. Remarkably
, PM3 indicates the formation of a sigma-type radical anion in the cas
e of the reduction of the bromobenzene derivatives.