Ultra-stable metal-organic frameworks (MOFs), MIL–53 and UiO–66 containing 2-iodoterephthalate have proven to be effective catalysts for the oxidation of hydroquinone derivatives. A multivariate approach was utilized to ensure sufficient internal space for reagent and terminal oxidant diffusion. The catalytic frameworks could be recycled, but in the case of UiO-66, the catalyst degraded as a result of particle agglomeration. The substrates were limited in scope in two ways: 1) size and 2) oxidation potential.<br/>In order to overcome the limitations of these systems, the larger frameworks DUT-5 and UiO-67 were prepared by functionalizing biphenyl-4,4′-dicarboxylic acid with iodine and adopting the same multivariate approach. The increased pore size of DUT-5 and UiO-67 allows for larger substrates as well as a larger variability of substrates. The enhanced catalytic ability of the larger multivariate metal-organic frameworks (MTV-MOFs) towards the oxidation of various alcohols to ketones or aldehydes is discussed. Recyclability tests for the multivariate MOFs showed stability over multiple catalytic trials. Hypervalent iodine (III) species in the MOFs was made <i>in situ</i> upon addition of a terminal oxidant as probed by XPS. Strategies for attaining I(V) species will be discussed.

Hypervalent iodine (III) supporting UiO-67 and DUT-5 as catalysts for the oxidation of aromatic diols

256th National Meeting (2018)

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