X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting.

X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear Mn(IV) complexes [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+). These compounds are known to effect C-H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing Mn(IV)-hydroxo versus Mn(IV)-oxo motifs, as they differ by only a proton. Simulations of 5 K EPR data, along with analysis of variable-temperature EPR signal intensities, allowed for the estimation of ground-state zero-field splitting (ZFS) and (55)Mn hyperfine parameters for both complexes. From this analysis, it was concluded that the Mn(IV)-oxo complex [Mn(IV)(O)(OH)(Me2EBC)](+) has an axial ZFS parameter D (D = +1.2(0.4) cm(-1)) and rhombicity (E/D = 0.22(1)) perturbed relative to the Mn(IV)-hydroxo analogue [Mn(IV)(OH)2(Me2EBC)](2+) (|D| = 0.75(0.25) cm(-1); E/D = 0.15(2)), although the complexes have similar (55)Mn values (a = 7.7 and 7.5 mT, respectively). The ZFS parameters for [Mn(IV)(OH)2(Me2EBC)](2+) were compared with values obtained previously through variable-temperature, variable-field magnetic circular dichroism (VTVH MCD) experiments. While the VTVH MCD analysis can provide a reasonable estimate of the magnitude of D, the E/D values were poorly defined. Using the ZFS parameters reported for these complexes and five other mononuclear Mn(IV) complexes, we employed coupled-perturbed density functional theory (CP-DFT) and complete active space self-consistent field (CASSCF) calculations with second-order n-electron valence-state perturbation theory (NEVPT2) correction, to compare the ability of these two quantum chemical methods for reproducing experimental ZFS parameters for Mn(IV) centers. The CP-DFT approach was found to provide reasonably acceptable values for D, whereas the CASSCF/NEVPT2 method fared worse, considerably overestimating the magnitude of D in several cases. Both methods were poor in reproducing experimental E/D values. Overall, this work adds to the limited investigations of Mn(IV) ground-state properties and provides an initial assessment for calculating Mn(IV) ZFS parameters with quantum chemical methods.