reflect usage leading

score quantitative measure

selective hydrogenation

active sites

Molecular Catalysis

• Hf-MOF-808 with excellent activity and specific selectivity on the hydrogenation. • The reaction mechanism explored by DFT computations. • The specific reaction selectivity explained by the structure of transition state. Hf-MOF-808 exhibits excellent activity and specific selectivity on the hydrogenation of carbonyl compounds via a hydrogen transfer strategy. Its superior activity than other Hf-MOFs is attributed to its poor crystallinity, defects and large specific surface area, thereby containing more Lewis acid-base sites which promote this reaction. Density functional theory (DFT) computations are performed to explore the catalytic mechanism. The results indicate that alcohol and ketone fill the defects of Hf-MOF to form a six-membered ring transition state (TS) complex, in which Hf as the center of Lewis stearic acid coordinates with the oxygen of the substrate molecule, thus effectively promoting hydrogen transfer process. Other reactive groups, such as –NO 2 , C = C, -CN, of inadequate hardness or large steric hindrance are difficult to coordinate with Hf, thus weakening their catalytic effect, which explains the specific selectivity Hf-MOF-808 for reducing the carbonyl group.

Hf-MOF catalyzed Meerwein−Ponndorf−Verley (MPV) reduction reaction: Insight into reaction mechanism