In a collaborative effort as part of the Inorganometallic Center for Catalyst Design we show that iron-based Metal Organic Framework (MOFs) materials take on properties similar to non-heme iron containing enzymes and readily activate alkanes via oxidative routes. Using a combination of X-ray absorption, Mössbauer, and infrared spectroscopy we report this reactivity in Fe-based MOFs is engendered by the transformation of Fe(II) sites reacting with oxidants to form Fe(IV)=O in kinetically-relevant steps and these Fe(IV)=O species subsequently reacting in radical-rebound type pathways to enable alkane oxyfunctionalization. The reaction kinetics and mechanism deduced by varying reactant concentration, temperature, and batch time compare well with DFT cluster calculations and validate a mechanism involving multiple antiferromagnetically-coupled high-spin iron centers in proximity to the active site.

Selective oxidation of light alkanes over iron species situated in the nodes of metal organic framework

ACS Fall 2021

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