Modulating the Energetics of C–H Bond Activation in Methane by Utilizing Metalated Porphyrinic Metal–Organic Frameworks

In recent years, much effort has been directed toward utilizing metal–organic frameworks (MOFs) for activating C–H bonds of light alkanes. The energy demanding steps involved in the catalytic pathway are the formation of metal-oxo species and the subsequent cleavage of the C–H bonds of alkanes. With the intention of exploring the tunability of the activation barriers involved in the catalytic pathway of methane hydroxylation, we have employed density functional theory to model metalated porphyrinic MOFs (MOF-525(M)). We find that the heavier congeners down a particular group have high exothermic oxo-formation enthalpies Δ H O and hence are associated with low N 2 O activation barriers. Independent analyses of activation barriers and structure–activity relationship leads to the conclusion that MOF-525(Ru) and MOF-525(Ir) can act as an effective catalysts for methane hydroxylation. Hence, Δ H O has been found to act as a guide, in the first place, in choosing the optimum catalyst for methane hydroxylation from a large set of available systems.