Coordinatively Unsaturated Hf-MOF-808 Prepared via Hydrothermal Synthesis as a Bifunctional Catalyst for the Tandem -Alkylation of Amines with Benzyl Alcohol.

The modulated hydrothermal (MHT) synthesis of an active and selective Hf-MOF-808 material for the -alkylation reaction of aniline with benzyl alcohol under base-free mild reaction conditions is reported. Through kinetic experiments and isotopically labeled NMR spectroscopy studies, we have demonstrated that the reaction mechanism occurs via borrowing hydrogen (BH) pathway, in which the alcohol dehydrogenation is the limiting step. The high concentration of defective -OH groups generated on the metallic nodes through MHT synthesis enhances the alcohol activation, while the unsaturated Hf, which acts as a Lewis acid site, is able to borrow the hydrogen from the methylene position of benzyl alcohol. This fact makes this material at least 14 times more active for the -alkylation reaction than the material obtained via solvothermal synthesis. The methodology described in this work could be applied to a wide range of aniline and benzyl alcohol derivates, showing in all cases high selectivity toward the corresponding -benzylaniline product. Finally, Hf-MOF-808, which acts as a true heterogeneous catalyst, can be reused in at least four consecutive runs without any activity loss.