RADICAL-ANIONS OF HALOSUBSTITUTED METHANES STRUCTURE AND CHEMICAL-REACTIVITY

The structure, as well as the formation and decomposition reactions, o f radical anions of halosubstituted methanes are investigated by the M NDO, AM1 and PM3 (UHF and RHF) methods. It is shown that the electron addition leads to a lowering of the T-d symmetry of CF4 and Cl-4. The geometry of other radical anions is similar to that of neutral parent molecules. After an electron transfer to halogen substituted methanes, the forming radical anions decompose by the cleavage of the C-Hal bon d. An increase in the number of Hal atoms, as well as a decrease in th e solvent polarity, enhance the radical anion stability. Decomposition with cleavage of the C-H bond is also possible, but only in a special environment, in particular, in electrochemical reactions on a Pt elec trode, which may adsorb the H atoms.