Multifunctional Catalysis of Nanosheet Defective Molybdenum Sulfide Basal Planes for Tandem Reactions Involving Alcohols and Molecular Hydrogen

Complementary to known reductive reactionsusing carbonylcompounds, straightforward domino synthetic processes involving alcoholsare established by applying a defect-engineered molybdenum sulfidecatalyst. Establishingtandem catalytic synthetic strategies basedon theuse of readily available, stable, and renewable feedstocks is of greatsignificant for the sustainable advancement of chemical-related industries.The key to success largely relies on applying efficient multifunctionalcatalysts that allow carrying out one-pot single-step synthesis. Inthis work, we have demonstrated that defect-engineered basal planesof a molybdenum sulfide nanomaterial ({Mo3S4}( n )) offer a multifunctional catalyticplatform for chemical process intensification. By applying this catalyst,besides borrowing hydrogen-type processes, herein exemplified forthe thioetherification of alcohols, we have also disclosed novel andrare coupling reactions requiring hydrogen activation and alcoholdehydrogenation processes in a one-pot fashion. More specifically,oxidized nucleophiles, such as o-dinitroarenes anddinitrophenyl disulfides, are reacted with alcohols in the presenceof H-2 to yield respectively benzimidazoles and benzothiazoles.The uncommon catalytic reactivity of {Mo3S4}( n ) arises from the presence of coordinativelyunsaturated molybdenum and sulfide species, which work as Lewis acidand Lewis basic sites, respectively. As suggested by in situ infrared(IR) spectroscopy investigations, the alcohol dehydrogenation involvesthe participation of both types of active sites while the H-2 dissociation takes place on coordinatively unsaturated sulfide species.