Journal of the American Chemical Society, Vol.141, No.31, 12187-12191, 2019
Highly Reactive Manganese(IV)-Oxo Porphyrins Showing Temperature-Dependent Reversed Electronic Effect in C-H Bond Activation Reactions
We report that Mn(IV)-oxo porphyrin complexes, Mn-IV(O)(TMP) (1) and Mn-IV(O)(TDCPP) (2), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, via an oxygen non-rebound mechanism. Interestingly, 1 with an electron-rich porphyrin is more reactive than 2 with an electron-deficient porphyrin at a high temperature (e.g., 0 degrees C). However, at a low temperature (e.g., -40 degrees C), the reactivity of 1 and 2 is reversed, showing that 2 is more reactive than 1. To the best of our knowledge, the present study reports the first example of highly reactive Mn(IV)-oxo porphyrins and their temperature-dependent reactivity in C-H bond activation reactions.