Hydrogen Atom Transfer Thermodynamics of Homologous Co(III)- and Mn(III)-Superoxo Complexes: The Effect of the Metal Spin State

[Image: see text] Systematic investigations on H atom transfer (HAT) thermodynamics of metal O(2) adducts is of fundamental importance for the design of transition metal catalysts for substrate oxidation and/or oxygenation directly using O(2). Such work should help elucidate underlying electronic-structure features that govern the OO–H bond dissociation free energies (BDFEs) of metal-hydroperoxo species, which can be used to quantitatively appraise the HAT activity of the corresponding metal-superoxo complexes. Herein, the BDFEs of two homologous Co(III)- and Mn(III)-hydroperoxo complexes, 3-Co and 3-Mn, were calculated to be 79.3 and 81.5 kcal/mol, respectively, employing the Bordwell relationship based on experimentally determined pK(a) values and redox potentials of the one-electron-oxidized forms, 4-Co and 4-Mn. To further verify these values, we tested the HAT capability of their superoxo congeners, 2-Co and 2-Mn, toward three different substrates possessing varying O–H BDFEs. Specifically, both metal-superoxo species are capable of activating the O–H bond of 4-oxo-TEMPOH with an O–H BDFE of 68.9 kcal/mol, only 2-Mn is able to abstract a H atom from 2,4-di-tert-butylphenol with an O–H BDFE of 80.9 kcal/mol, and neither of them can react with 3,5-dimethylphenol with an O–H BDFE of 85.6 kcal/mol. Further computational investigations suggested that it is the high spin state of the Mn(III) center in 3-Mn that renders its OO–H BDFE higher than that of 3-Co, which features a low-spin Co(III) center. The present work underscores the role of the metal spin state being as crucial as the oxidation state in modulating BDFEs.