-97 -93 kcal/mol), and Cu MOFs (ca. 11 -69 kcal/mol), respectively (Figure ). The range of DE(oxo) for Co SBUs is very wide compared to the other metals primarily due to two outliers at each extremum (Figure ). Omitting the Co SBU outliers, the ordering of DE(oxo) energies aligns with the oxo-wall theory that is applicable to tetragonal transition metal-oxo complexes, although our MOF SBUs have a greater variation in coordination geometries than those that were used to propose the oxo-wall theory (Supporting Information Figure ). Consistent with this theory, latetransition-metal oxo complexes formed on MOF SBUs are thermodynamically unstable because they have lower formal metal-oxo bond orders (Supporting Information Figure ). Thus, within our curated dataset, we identify previously overlooked Mn MOFs that form more stable metal-oxo intermediates than those formed by Fe MOFs. Prior work on methane to methanol catalysis, which focused on MOF families with experimentally demonstrated O2 chemisorption properties, showed that Fe MOFs exhibit the most favorable oxo formation. In this case, the studied MOFs usually shared a common structure, whereas our dataset includes more diverse coordination environments around the metal centers, leading to prediction of favorable oxo formation by the presently studied Mn MOFs. Our results also align with trends observed in transition metal complexes where homogeneous Mn catalysts also form the metal-oxo species more favorably than Fe catalysts. We find that DE(HAT) values span a narrower range compared to the DE(oxo) values, with most SBUs having DE(HAT) within a range of 0±20 kcal/mol (Figure ). Due to the existence of a universal nearly 1:1 Bronsted-Evans-Polanyi (BEP) relation between the HAT kinetic barrier height and DE(HAT), this also suggests that HAT from methane is relatively facile.