The calculated results in literatures for the decomposition of formic acid on Pt(111) into CO cannot rationalize the well-known easy CO poisoning of Pt-based catalysts.

DFT calculations show a clear picture of how a SO3H-functionalized imidazolium-based ionic liquid catalyzes the conversion of 5-HMF to LA.

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DFT calculations have been performed to illuminate the mechanism of cascade hydrogenation–cyclization of levulinic acid (LA) into γ-valerolactone (GVL) catalyzed by half-sandwich iridium complexes. It is shown that the favorable mechanism involves a heterolytic hydrogen cleavage for Ir–OH species to form a monohydride iridium species, concerted reduction of the CO unit of LA, hydrogen migration and dehydration to produce the iridium alkoxo complex, and cyclization of the iridium alkoxo complex to generate GVL. The presence of water and counterions are proposed to be important for the hydrogenation where the former works as a hydrogen donor and the latter acts as a hydrogen shuttle. Intriguingly, the cyclization process exploits a metal- and counterion-assisted concerted dehydration–cyclization mechanism different from the known ones that feature the intramolecular esterification of 4-hydroxyvaleric acid. The effectiveness of the half-sandwich iridium complex with the double-methoxy group on the bipyridine ligand-catalyzed system is attributed to the stronger electron-donating methoxy group, which is beneficial to increase the electron density at the Ir center and hence promote the Ir–H bond cleavage. In addition, the calculated free energy barrier for the cascade hydrogenation–cyclization catalyzed by the iridium complex with a dipyridylamine ligand is comparable with that promoted by the iridium complex with the double-methoxy group on the bipyridine ligand (24.8 vs 26.8 kcal/mol). The present work rationalizes the experimental findings and provides in-depth insights into the catalysis of the half-sandwich iridium complexes.