INTRAMOLECULAR ELECTRON TRANSFER AND DEHALOGENATION OF NITROAROMATIC ANION RADICALS.

Article abstract of DOI:10.1021/ja00341a003

A series of nitroaromatic compounds, containing Cl, Br or tosyl groups at various positions, were synthesized and studied by pulse radiolysis in aqueous alcohol solutions. One-electron reduction of the compounds produces the anion radicals which then undergo an intramolecular electron transfer and eliminate X** minus (Cl** minus , Br** minus , or TsO** minus ). The rates of X** minus elimination vary over six orders of magnitude and are affected by the C-X bond dissociation energies, the size and nature of the group bridging the X with the pi system, and the relative positions of these groups. Intramolecular electron transfer through space is also demonstrated. Refs.