Nanolayered Co-Mo-S Catalysts for the Chemoselective Hydrogenation of Nitroarenes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acscatal.7b00170[EN] Nanolayered molybdenum disulfide cobalt-promoted materials (Co-Mo-S) have been established as chemoselective catalysts for thehydrogenation of nitroarenes under relatively mild conditions. Co-Mo-S catalysts have been prepared by a one-pot hydrothermal synthesis that allows the formation of unsupported catalysts with a large number of active sites per unit volume. Via application of these catalysts, the hydrogenation of the nitro functionality has been performed selectively in the presence of double and triple bonds, aldehydes, ketones, and carboxylic acid derivative groups, thus affording the corresponding anilines in good to excellent yields. Interestingly, the partial hydrogenation of some dinitroarenes has also been successfully accomplished. In addition, its catalytic performance has been evaluated for the preparation of the bioactive compound paracetamol through a one-pot direct hydrogenative amidation reaction.The financial support of the European Union (FP7-NMP-2013-EU-Japan-604319-NOVACAM) is gratefully acknowledged. I.S. thanks Spanish MINECO for a "Formacion Postdoctoral" fellowship. The authors also thank the Microscopy Service of Universitat Politecnica de Valencia for kind help with TEM and STEM measurements.Sorribes-Terrés, I.; Liu, L.; Corma Canós, A. (2017). Nanolayered Co-Mo-S Catalysts for the Chemoselective Hydrogenation of Nitroarenes. ACS Catalysis. 7(4):2698-2708. https://doi.org/10.1021/acscatal.7b00170S269827087

Funcionalización Química de Calcogenuros Clúster de Molibdeno con Simetría C3 dirigida hacia sus aplicaciones en catálisis y el diseño de materiales

This thesis describes the synthesis, characterization and properties of a novel family of cuboidal homo- and heterobimetallic molybdenum chalcogenide clusters. The synthetic strategy employed to prepare these novel cluster species is based on the chemical functionalization of the trimetallic Mo3Q4 (Q = S, Se) core by varying the nature of the outer ligands or by incorporating a second transition metal fragment to obtain cubane-type heterobimetallic clusters. Both strategies are directed towards the isolation of functional molecular complexes with potential applications in catalysis, molecular electronic or as building blocks of higher nuclearity materials. In this regard, the immobilization of tailor functionalized molecular clusters into mesoporous silica is also presented. Three different approaches have been undertaken towards the functionalization of Mo3Q4 (Q = S, Se) cluster complexes. The first one is based on the substitutional reactivity of the Mo-halide functional groups. The second one consists on the incorporation of a second transition metal to access cubane-type heterobimetallic Mo3M’Q4 (M’ = Fe, Cu; Q = S) compounds. Finally, the third one is based on the coordination of diphosphane ligands of different nature