Engineering Mono- vs Dinuclear Iron(II)-Active Sites to Steer Liquid Oxygenate Selectivity in Methane Oxidation Pathways Using O₂

The selective oxidation of methane to liquid oxygenates using O₂ under mild conditions remains a grand challenge due to the chemical inertness of methane and the competing thermodynamically favored overoxidation. We report the development of well-defined mono- and dinuclear bipyridyl Fe(II) hydroxyl species within a porous metal-organic framework [MOF-253(Al)], which enable methane oxidation by O₂ via distinct oxidation pathways with exceptionally high product selectivity. The MOF-supported dinuclear Fe(II) catalyst (MOF-253-Fe₂) having a [(bpy)Fe^II(μ₂-OH)(OH)]₂ active site achieves 100% liquid selectivity toward acetic acid with a productivity of 2757 mmol_CH3CO2H mol_Fe^-1 h^-1 at 160 °C. In comparison, the MOF-supported mononuclear (bpy)Fe^II(OH)₂ catalyst (MOF-253-Fe) exhibits a remarkably high methanol productivity of 6060 mmol_CH3OH mol_Fe^-1 h^-1 with 96% selectivity in the aqueous phase at 95 °C. Spectroscopic and mechanistic studies suggested that the confinement and stabilization of [(bpy)Fe^II(μ₂-OH)(OH)]₂ active site in the MOF-253-Fe₂ framework facilitate redox cooperativity and multielectron transfer, enabling sequential O₂ activation, methane C-H bond activation, followed by C-C bond coupling with <i>in situ</i>-generated CO to yield acetic acid through the formation of [(bpy)Fe^III(μ₂-OH)(OH)₂]₂ catalytic intermediate. In contrast, the MOF-253-Fe catalyst lacks such synergy but efficiently promotes methane C-H hydroxylation to yield methanol. This work underscores the importance of active site engineering in governing product selectivity and provides valuable insights into the design of advanced catalysts for selective methane functionalization.