Clarity as to the role of metal identity and oxidation state in effecting redox and acid-catalyzed turnovers is oftentimes precluded by a high degree of heterogeneity in site speciation, a limitation that can be overcome through the use of well-defined poly-metal clusters hosted by metal organic framework materials- accomplished in the present case using MIL-100(M) for the low temperature oxidation of methane with N2O. Transient kinetic data point to a) methoxy species mediating methane conversion, b) partial and deep oxidation occurring over metal sites distinct in oxidation state, c) chromium clusters amplifying the propensity toward C-C bond formation, and d) the relative velocity of propagation of water and methanol concentration fronts playing a determinative role in maximizing C2 oxygenate selectivity. The study captures the utility of using classes of materials inherently endowed with a high level of definition and uniformity in advancing the elucidation of structure-catalytic property relationships.