Far infrared spectroscopy (FIR) lies in the low spectral energy region. It has been demonstrated to be well suited to distinguish the fundamental differences in the coordination chemistry of metal chlorides in the presence of model compounds with different oxygen sources, hydroxyl, carbonyl, glycolaldehyde group and H2O. In our recent studies, reaction kinetics was applied to quantify the coordination strength of metal chlorides with model compounds containing oxygen sources based on the FIR results. Our latest FIR results combining with kinetics analysis revealed that V(III) ion was preferentially coordinated by carbonyl group and Zr (IV) ion was most strongly coordinated by hydroxyl group (See Table 1). Thus V(III) ion has the potential to catalyze aldol condensation by effective carbonyl activation. Zr (IV) could be used to catalyze halogenations of alcohols by hydroxyl activation. In this work, two industrially important reactions were studied to verify our hypotheses. The experimental results confirmed the excellent performance of VCl3 in the condensation of furfural with acetone with over 90% yield to 4-(2-furyl)-3-buten-2-one, and 1,5-bis-(2-furanyl)-1,4-pentadien-3-one in 1-butyl-3-methylimidazolium chloride ionic liquid. And ZrCl4 showed the best catalytic performance in halogenations of benzyl alcohol with 83% conversion and 97% selectivity to benzyl iodine. The catalytic results were consistent with the FIR results based on kinetics analysis.

Knowledge driven catalyst screening using In-situ far infrared spectroscopy

255th National Meeting (2018)

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