Tkachenko B. Cage Hydrocarbons in the Reactions with Transition Metal Based Electrophiles

It has been found, that metal-oxo-oxidants react with strong C-C bonds in accordance to the oxidative mechanism, and follow the molecule-induced homolytic path with weak ones (which have significant biradical nature). It has been conclu- ded, that the selectivity of substitutions is controlled by a charge transfer from hydrocarbon to electrophile and is deter- mined by the structure of the hydrocarbon radical-cation. The reaction of С-С bonds was studied for the first time. The dis- tinct differences between the mechanisms of alkane activa- tion with metal-oxo-reagents and dioxiranes is reveled. It has been shown, that common mechanism (molecule-induced homolysis) was followed only for the reactions of weak C-C bonds. For the reactions of dioxiranes with strong -bonds of alkanes concerted insertion is operative.