Mononuclear Bipyridyl-Iron(III) hydroxide in Metal-Organic Framework for selective Alkene Oxidation​

Journal of Molecular Chemistry

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The selective oxidation of styrene to value-added products such as benzaldehyde and benzoic acid is of significant industrial importance. We report the design of a single-site iron catalyst supported on a bipyridine-functionalized metal-organic framework, bpy-UiO-Fe(OH)₃, which enables selective oxidation of styrene into benzaldehyde or benzoic acid using H₂O₂ as the oxidant. Systematic optimization of solvent composition, temperature, and reaction time revealed that benzaldehyde can be obtained with 100% selectivity at 80 °C in 8 h, while prolonged reactions furnish benzoic acid in high yields. Control experiments confirmed the heterogeneous, single-site nature of the catalyst, which remained structurally robust and can be recycled at least 3 times with negligible Fe leaching. Mechanistic studies suggest a non-radical pathway involving epoxide and diol intermediates prior to carbon-carbon bond cleavage. This work demonstrates the potential of MOF-supported abundant-metal catalysts for sustainable oxidation of alkenes under environmentally benign conditions.