The Oxidative Mechanism in Electrophilic CH Activation: The Case of CH2F2 and CH2Cl2.

The H.-atom transfer (HAT) reaction is investigated in the gas phase, starting from two different entrance channels, O2.+/CH2X2 and CH2X2.+/O2 (X=F, Cl), that correspond to a step of hydride transfer and to HAT, respectively. Analysis of the spin and charge along the reaction pathway shows that HAT occurs through the same reacting configuration, irrespective of whether the reactants are formed within the complex or are free isolated species. [ABSTRACT FROM AUTHOR]