Oxyl radical character in the MnO group of the title system is shown from a density functional theory study to be essential for efficient C−H cleavage, which is a key step in C−H oxidation. Since oxyl species have elongated Mn−O bonds relative to the more usual oxo species of type MnO, the normal expectation would be that high trans-influence ligands X should facilitate oxyl character by elongating the Mn−O bond and thus enhance both oxyl character and reactivity. Contrary to this expectation, but in line with the experimental data (Jin, N.; Ibrahim, M.; Spiro, T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416), we find that reactivity increases along the series X = O2−