Exploring mechanistic routes for light alkane oxidation with an iron-triazolate metal-organic framework

In this work, we computationally explore the formation and subsequent reactivity of various iron-oxo species in the iron-triazolate framework Fe₂(μ-OH)₂(bbta) (H₂bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) for the catalytic activation of strong C-H bonds. With the direct conversion of methane to methanol as the probe reaction of interest, we use density functional theory (DFT) calculations to evaluate multiple mechanistic pathways in the presence of either N₂O or H₂O₂ oxidants. These calculations reveal that a wide range of transition metal-oxo sites - both terminal and bridging - are plausible in this family of metal-organic frameworks, making it a unique platform for comparing the electronic structure and reactivity of different proposed active site motifs. Based on the DFT calculations, we predict that Fe₂(μ-OH)₂(bbta) would exhibit a relatively low barrier for N₂O activation and energetically favorable formation of an [Fe(O)]²⁺ species that is capable of oxidizing C-H bonds. In contrast, the use of H₂O₂ as the oxidant is predicted to yield an assortment of bridging iron-oxo sites that are less reactive. We also find that abstracting oxo ligands can exhibit a complex mixture of both positive and negative spin density, which may have broader implications for relating the degree of radical character to catalytic activity. In general, we consider the coordinatively unsaturated iron sites to be promising for oxidation catalysis, and we provide several recommendations on how to further tune the catalytic properties of this family of metal-triazolate frameworks.