Catalytic Hydrogenation of Azobenzene in the Presence of a Cuboidal Mo₃S₄ Cluster via an Uncommon Sulfur-Based H₂ Activation Mechanism

Abstract

Crystal structure determination of [Mo 3 CuS 4 Cl 4 (dmen) 3 ](CuCl 2

Metal–metal bonds in polyoxometalate chemistry

“…From recent studies in a comparable system, the molybdenum triad would also be expected to undergo reversible covalent dynamics, enabling the continuation of the catalytic cycle. 117 Formal replacement of the oxo ligands with less charged polyalkoxometalates ligands can allow higher reductions while maintaining a relatively low overall negative charge of the polyalkoxometalates.…”

Defective Ultrathin ZnIn2S4 for Photoreductive Deuteration of Carbonyls Using D2O as the Deuterium Source

“…[ 19 ] Furthermore, density functional theory (DFT) suggests that the surface sites, especially for the vacancy have a great impact on the H* adsorption energy of transition‐metal chalcogenides. [ 20 ] Given that the efficient charge separation and H*/D* generation are favorable for photocatalytic hydrogenation/deuteration, these results unambiguously prove that engineering semiconductors with surface defects could improve charge separation, expose more active sites, and create long‐lived active species for our target photoreductive deuteration reactions without the dependence on noble metal co‐catalysts.…”

“…Among the three semiconductors, ZIS possesses the least reduction power and strongest H* adsorption, thus leading to inferior HER performance while better hydrogenation capability. [ 20 , 22 ] Hence, the subsequent work will focus on ZIS as the desirable photocatalyst.…”

“…It is expected that moderate adsorption energy of H* is favored to promote the hydrogenation reaction. [ 14 , 20 , 23 ] Strong H* adsorption may inhibit the adsorption and formation of other reaction intermediates, whereas weak H* adsorption leads to serious HER. [ 19 , 33 , 39 ] In this respect, the adsorption of H/D* on top‐Zn and bridge sites in D‐ZIS seems to be beneficial for the target hydrogenation/deuteration reactions.…”

Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines

“…Lin group reported hydrogenation of azobenzene and hydrazobenzene to aniline using hydrogen pressure by a heterogeneous process using a supported cobalt catalyst (Scheme 2, b) [8] . Very recently (during preparation of this manuscript), another heterogeneous procedure for the catalytic hydrogenation of azobenzene using Mo 3 S 4 clusters has been reported [9] . Cleavage of azo derivatives into the corresponding amine(s) via transfer hydrogenation or using hydrogen donors were reported but both these reports also need stoichiometric additives [10] .…”