A theoretical study into a trans-dioxo MnV porphyrin complex that does not follow the oxygen rebound mechanism in C–H bond activation reactions

Abstract

Previous experimental results revealed that the C–H bond activation reaction by a synthetic trans-dioxo Mn^V porphyrin complex, [(TF₄TMAP)OMn^VO]³⁺, does not occur via the well-known oxygen rebound mechanism, which has been well demonstrated in Fe^IVO porphyrin π–cation radical reactions. In the present study, theoretical calculations offer an explanation through the energetics involved in the C–H bond activation reaction, where a multi-spin state scenario cannot be excluded.