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A Comparative Study of Structurally Related Homogeneous Ruthenium and Iron Catalysts for the Hydrogenation of Levulinic Acid to γ‐Valerolactone

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The conversion of levulinic acid to -valerolactone was investigated by employing the homogeneous Shvo catalyst (Ru-1) and iron Knolker-type catalysts, in order to evaluate the possibility to replace ruthenium with… Click to show full abstract

The conversion of levulinic acid to -valerolactone was investigated by employing the homogeneous Shvo catalyst (Ru-1) and iron Knolker-type catalysts, in order to evaluate the possibility to replace ruthenium with cheap, earth-abundant iron for this catalytic reaction. While the ruthenium-catalyzed reactions readily proceed, the activating agent required for the iron complex was found to interfere with the levulinic acid. This problem could be circumvented by pre-activating the original Knolker complex (Fe-1) into the corresponding dicarbonyl mono-acetonitrile iron species (Fe-3). The pre-activated iron catalyst deactivated after a few turn-overs in transfer hydrogenation reactions with isopropanol, however, highly improved -valerolactone yields were achieved under H2 pressure to a notable maximum of 570 turn-overs for Fe-3. Nevertheless, comparative screening experiments with various solvents and kinetic studies showed that Ru-1 is still superior over Fe-3 in terms of catalytic activity.

Keywords: ruthenium; iron; acid valerolactone; levulinic acid

Journal Title: European Journal of Inorganic Chemistry
Year Published: 2017

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