Molybdenum sulfide cluster catalysts in hydrogenation and dehydrogenation reactions: a combined theoretical and experimental study

Abstract

This doctoral thesis addresses the synthesis, structural characterization and applications as homogeneous catalysts of molybdenum sulfide clusters decorated with ligands containing amino groups. In particular, hydrogenation and dehydrogenation processes catalyzed by these compounds have been investigated. The synthesis of a series of new imidazolyl amino Mo3S4 clusters is presented, and their catalytic activity is assessed in the stereoselective semihydrogenation of internal alkynes to obtain the (Z)-alkene. Besides, the potential of these and other closely related Mo3S4 clusters for the catalytic hydrogen production from formic acid is shown. The best results are found for aminophosphine-based Mo3S4 clusters. Both transformations have been tackled using an integrative approach that combines experimental methodologies with theoretical calculations. Such approach has allowed us to postulate hydrogenation and dehydrogenation reaction mechanisms based on solid evidence.