The competition between ortho and ipso attacks in the reactions of O( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si29.svg" display="inline" id="d1e502"> <mml:msup> <mml:mrow/> <mml:mrow> <mml:mn>3</mml:mn> </mml:mrow> </mml:msup

We present a density functional theory characterization of the adiabatic triplet potential energy surfaces for the reactions of atomic oxygen with seven functionalized arenes (aniline, phenol, 1,3-diphenylpropane, diphenyl ether, propylbenzene, formanilide, and benzonitrile) to characterize the competition between ortho and ipso additions. Ortho and ipso additions give rise to O/H or O/R exchange channels, respectively, where R represents the functional groups of the substituted arenes. Our results show that the ortho position is favored in all cases, except for phenol, where ortho competes with ipso. The study provides a useful guide for future experimental investigations.