The energy of methanol release, DE(release), is an important quantity in methane to methanol catalysis because it can become rate-limiting and is also indicative of methanol overoxidation in the presence of oxidant at the active site. There is limited overall or metalspecific correlation between DE(release) and DE(oxo) or DE(HAT) (Figure ). The methanol release energies are consistently high across all SBUs regardless of metal (Figure ). This could be due to strong electrostatic attraction between the metal center and the bound methanol that is influenced by the overall positive charge on the SBU cluster models. The high methanol release energies are consistent with known challenges of methanol desorption from the active site. We compare DE(oxo), DE(HAT), and DE(release) reaction energies in our dataset to those computed for Fe-MOF-74, which is known to catalyze ethane hydroxylation. We find that Mn MOFs in our dataset form more stable metal-oxo intermediates than Fe-MOF-74 while having comparable HAT and methanol release energies, motivating a further investigation of our MOFs for methane to methanol activity (Supporting Information Figure and Table ). Despite potential limitations in completing the catalytic cycle due to high methanol release energies, we identify three Mn MOFs with the most promising combination of DE(oxo), DE(HAT), and DE(release) for detailed characterization of the methane to methanol catalytic cycle. These three Mn MOFs are [Mn(HTPA)(DMF)2]n•H2O (also referred to as FIR-34, CSD refcode DADLEC), [Mn3(ABTC)2(H2O)4•9.5H2O]n (CSD refcode EBUREA), and [Mn2(BDC)2(DMF)2]n (CSD refcode LUSHOX04) (Figure ). These MOFs have been studied for their unique structural and magnetic properties but, to our knowledge, have yet to be tested for catalytic applications or studied computationally. For the three selected MOF SBUs, we characterize the full reaction coordinate (i.e., both transition states and reaction intermediates) with thermodynamic corrections for the radical rebound mechanism of methane to methanol catalysis using N2O as an oxidant (Figure and Supporting Information Texts S2 and S3 and Tables ). While we compute transition states for oxo formation and HAT, we model it as an unassisted dissociation and so we neglect any kinetic barrier. We also assume the rebound of the methyl radical following C-H activation to be barrierless and omit explicit calculation of a barrier for this step. The DADLEC MOF, which has a square planar geometry at the active Mn site, undergoes a concerted oxo formation step without the formation of a stable N2O bound intermediate as confirmed by intrinsic reaction coordinate (IRC) calculations (Figure , Supporting Information Figure and Text S2). The three-coordinate trigonal pyramidal Mn center in the SBU of LUSHOX04 instead exhibits stepwise oxo formation. Here, LUSHOX04 first forms a complex with N2O, which is assumed to be barrierless since N2O retains its linear geometry in this complex, followed by cleavage of the O-N bond to form the metal-oxo intermediate (Figure , Supporting Information Figure and Text S2). The IRC calculations on EBUREA also suggest a stepwise oxo formation, but EBUREA forms a complex with N2O in which N2O assumes a bent geometry (Supporting Information Figures and and Text S2). Although we expect this complexation step to have a barrier due to the energetic cost of bending the N-N-O angle in N2O, we were unable to locate a transition state associated with complexation for EBUREA and thus do not consider this MOF further in our analysis.