Chemoselective Hydrogenation of Nitroarenes Catalyzed by Molybdenum Sulphide Clusters

Abstract

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Studies on the Reactivity of the [W3S4Br3(edpp)3]+ [edpp = (2‐aminoethyl)diphenylphosphine] Cluster Cation towards Bases: The Active Role of the Amino Group

“…This is illustrated clearly by our mechanistic studies on the proton‐transfer reactions between diphosphino trinuclear M 3 S 4 (M = Mo, W) hydride clusters and acids, which support the initial formation of dihydrogen‐bonded adducts that then evolve to substitution products with H 2 release . As previously mentioned, this finding led us to investigate the catalytic activity of these systems in the reduction of nitro derivatives to obtain amines selectively in high yields …”

“…Trinuclear molybdenum sulfide cluster complexes catalyze the photogeneration of hydrogen from water if they are coupled to a semiconductor such as p‐type silicon or titanium dioxide , . In collaboration with the Beller group, some of us have recently investigated the catalytic performances of Mo 3 S 4 complexes functionalized with diphosphine, diamine and diimine ligands in the hydrogenation and transfer hydrogenation of nitroarenes . Moreover, group‐six M 3 S 4 clusters also catalyze the selective hydrodefluorination of pentafluoropyridine at the para position with silanes as the hydrogen source , …”

Bifunctional Pincer Catalysts for Chemoselective Transfer Hydrogenation and Related Reactions

“…[17k], Some promising examples of homogeneous transfer hydrogenation of nitroarenes using iron, ruthenium, cobalt, and molybdenum catalysts are paving the way to the development of an environmentally benign, sustainable, and waste‐economical industry. Despite this progress, the efficiency of homogeneous transfer hydrogenation of nitro groups needs to be improved, especially in terms of chemoselectivity because the desired reduction of nitroarenes to amines is often accompanied by incomplete reductions to hydroxylamines or azocompounds, as well as a competitive reduction of vulnerable functional groups such as halides, carbonyls, or nitriles …”

Benchmarking of DFT methods using experimental free energies and volumes of activation for the cycloaddition of alkynes to cuboidal Mo3S4 clusters

“…The cluster [Mo 3 S 4 Cl 3 (dmen) 3 ](BF 4 ), [ 1 ](BF 4 ), was prepared according to literature procedures. [ 14,15 ] All other chemicals were of reagent grade and commercially available. They were used as received.…”