Transition Structures for One Step Nonconcerted Oxygen Insertion Mechanism of Oxidation of Alkanes with Trifluoroperoxyacetic acid.

High level calcns. (UB3LYP/6-31G*) on the oxygen insertion by trifluoroperoxyacetic acid (TFPA) into methane and isobutane C-H bonds strongly supports the viability of a one step nonconcerted mechanism. That is, the O-H bond forms first and the C-O bond formation commences afterwards, but only one first order saddle point, exhibiting high diradical character and strong polarization, is present on the energy profile of the min. energy path. No minima corresponding to intermediates were located.