The central role of oxo clusters in zirconium-based esterification catalysis

Data of the figures in the publication "The central role of oxo clusters in zirconium-based esterification catalysis".DOI: https://doi.org/10.1002/smsc.202400369

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Figure 1: Structural representation of catalysts used in this article. A) Nanocrystal (ZrO2 ), B) Metal-organic framework (UiO-66), (C) Zr6 oxo cluster (Zr6-acetate) and D) Zr12 oxo cluster (Zr12-acetate)

Figure 2: Catalytic esterification of oleic acid with ethanol in ortho-dichlorobenzene (o-DCB). The catalyst is either Zr12-oleate, ZrO2 nanocrystals or the MOF UiO-66. The reactions were performed in triplicate.

Figure 3: Catalytic esterification, comparing Zr12 oxo clusters and UiO-66, for different carboxylic acid substrates. The conditions are identical to Figure 1: 120 °C, 12 mol% zirconium, 0.2 M carboxylic acid, molecular sieves, and four equivalents of ethanol.

Figure 4: Catalytic esterification of oleic acid with hexanol. The reaction is either done in mesitylene (using four equivalents hexanol), without mesitylene (using four equivalents hexanol), or without mesitylene and a reduced 1.2 equivalents of hexanol. In the latter case, we recovered the catalyst and used this for a second catalytic reaction. The dotted line corresponds to the maximum yield that can be obtained when excluding the oleate ligands on the catalyst surface.

Figure 5: PDF refinement for A) Zr12-oleate cluster before catalysis, and after the first and second round of catalysis, B) and for catalyst recovered after 30 min with and without molecular sieves using Zr(OR)4 as the catalyst. The values in square brackets correspond to the ratio of monomer to dimer-cluster in the fit. The refinement is performed using both Zr6- and Zr12-propionate structures obtained from the single crystal structure (CCDC 604529).

Figure S1 - S24: Figures from Supporting Information.