Anderson-type polyoxometalate-based metal-organic framework as an efficient heterogeneous catalyst for selective oxidation of benzylic C-H bonds

Oxidative transformation of benzylic C-H bonds into functional carbonyl groups under mild conditions represents an efficient method for the synthesis of aromatic carboxylic acids and ketones. Here we report a high-efficiency catalyst system constructed from an Anderson-type polyoxometalate-based metal-Organic framework (POMOF-1) and N-hydroxyphthalimide (NHPI) for selective oxidation of methylarenes and alkylarenes under 1 atm O2 atmosphere. POMOF-1 exerted a synergistic effect originating from the well-aligned Anderson {CrMo6} clusters and Cu centers within the framework, and this entailed good cooperation with NHPI to catalyze the selective oxidation. Accordingly, the reactions exhibit good tolerance and chemical selectivity for a wide range of substrates bearing diverse substituent groups, and the corresponding carboxylic acids and ketones were harvested in good yields under mild conditions. Mechanism study reveals that POMOF-1 worked synergistically with NPHI to activate the benzylic C-H bonds of substrates, which are sequentially oxidized by oxygen and HOO to give rise to the products. This work may pave a way to design high-efficiency catalysts by integration of polyoxometalate-based materials with NPHI for challenging C-H activation. Self-assembly of Anderson-type polyoxometalate {CrMo6} with Cu2+ and bistriazole L affords POMOF-1 that works cooperatively with NPHI for oxidative transformation of benzylic C-H bonds into carbonyl compounds.