Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes

Manganese(IV)-oxo complexes are often invoked as intermediates in Mn-catalyzed C-H bond activation reactions. While many synthetic Mn^IV -oxo species are mild oxidants, other members of this class can attack strong C-H bonds. The basis for these reactivity differences is not well understood. Here we describe a series of Mn^IV -oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the Mn^IV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K-edge X-ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen-atom and oxygen-atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these Mn^IV -oxo complexes, the rate enhancements are correlated with both 1) the energy of a low-lying ⁴ E excited state, which has been postulated to be involved in a two-state reactivity model, and 2) the Mn^III/IV reduction potentials.