Shubina T. Quantym-chemical study of alkane activation with electrophiles

Geometries and reaction paths for the radical cations, which form after the ionization of model cage compounds were analyzed. Possible fragmentation pathways for the hydrocarbon radical cations (breaking the C-H and C-C bonds) in the gas phase and in condensed state were studied. The key intermediates and transition structures were loca- lized in the reactions of the C-H bonds with carbocations and positivated halogens to estimate the kinetic isotopic effects (KIE), activation barriers and reaction orders. The linear geometries of the transition structures as well as significant charge transfer from alkane to the reagent is observed (H-coupled electron-transfer). Reactions with uncharged oxidizers (metal-oxo reagents) proceed via similar mechanism.