Reactive Intermediates in PET Reactions

Single bond fragmentations within high energy intermediates generated via PET take place almost exclusively at the radical ion stage. Although in principle 

Radical ions may be divided into two groups [72] 1) a radical ions, wherein the unpaired electron resides formally in a a orbital (one-electron bond radical cation) or a a orbital (three-electron bond radical anion) of the scissile bond, and 2) n radical ions, where the unpaired electron is delocalized over a w-system (removal of a non-bonding electron leads to a zr-like radical cation). The n radical ions are most frequently encountered in PET systems. In such radical ions the unpaired electron is initially highly localized on one side of the scissile bond and there are two formal ways in which electrons can be apportioned to 

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