Acceptorless Dehydrogenation Of N-heterocycles Research Articles

Dual role of graphene as support of ligand-stabilized palladium nanoparticles and carbocatalyst for (de)hydrogenation of N-heterocycles

The hybrid material composed of palladium nanoparticles (PdNPs) functionalized with N-heterocyclic carbene ligands (NHCs) immobilized onto the surface of reduced graphene oxide (rGO) results in an efficient catalytic material towards hydrogenation and dehydrogenation of N-heterocycles. The rGO plays a dual role by acting as a carbocatalyst in acceptorless dehydrogenation of N-heterocycles and as a support for the palladium nanoparticles facilitating its interaction with molecular hydrogen turning this hybrid material into an effective hydrogenation catalyst. Hot filtration experiments support the heterogeneous nature of the process underlining the strong interaction of palladium nanoparticles with the graphene enabled by π-interactions of the ligand with the support. The mild conditions used in both transformations of this system without requiring any additives facilitates its potential application in hydrogen storage technologies in the form of liquid organic hydrogen carriers (LOHCs). At the same time, the hybrid material is a robust and efficient catalytic platform that can be recovered and reused up to eight runs in both transformations without significant deactivation. The use of a single solid catalysts that is recyclable in hydrogen conversion and reconversion through (de)hydrogenation of N-heterocycles paves the way for the development of efficient hydrogen storage materials.

B,F Co-Doped Carbocatalysts with Dual-Active-Sites for Acceptorless Dehydrogenation of N-Heterocycles Under Room Temperature

B,F Co-Doped Carbocatalysts with Dual-Active-Sites for Acceptorless Dehydrogenation of N-Heterocycles Under Room Temperature

Reduced Graphene Oxides as Carbocatalysts in Acceptorless Dehydrogenation of N-Heterocycles.

The catalytic properties of graphene-derived materials are evaluated in acceptorless dehydrogenation of N-heterocycles. Among them, reduced graphene oxides (rGOs) are active (quantitative yields in 23 h) under mild conditions (130 °C) and act as efficient heterogeneous carbocatalysts. rGO exhibits reusability and stability at least during eight consecutive runs. Mechanistic investigations supported by experimental evidence (i.e., organic molecules as model compounds, purposely addition of metal impurities and selective functional group masking experiments) suggest a preferential contribution of ketone carbonyl groups as active sites for this transformation.

Geometric and electronic effects on the performance of a bifunctional Ru2P catalyst in the hydrogenation and acceptorless dehydrogenation of N-heteroarenes

The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N-heterocycles is a challenge. In this study, Ru2P/AC effectively promoted reversible transformations between unsaturated and saturated N-heterocycles affording yields of 98% and 99%, respectively. Moreover, a remarkable enhancement in the reusability of Ru2P/AC was observed compared with other Ru-based catalysts. According to density functional theory calculations, the superior performance of Ru2P/AC was ascribed to specific synergistic factors, namely geometric and electronic effects induced by P. P greatly reduced the large Ru-Ru ensembles and finely modified the electronic structures, leading to a low reaction barrier and high desorption ability of the catalyst, further boosting the hydrogenation and acceptorless dehydrogenation processes.

Iridium-Catalyzed Acceptorless Dehydrogenation of N-Heterocycles and Hydrogenation of N-Hetarenes

Iridium-Catalyzed Acceptorless Dehydrogenation of N-Heterocycles and Hydrogenation of N-Hetarenes

Hydrogenation or Dehydrogenation of N-Containing Heterocycles Catalyzed by a Single Manganese Complex.

A highly chemoselective base-metal catalyzed hydrogenation and acceptorless dehydrogenation of N-heterocycles is presented. A well-defined Mn complex operates at low catalyst loading (as low as 2 mol %) and under mild reaction conditions. The described catalytic system tolerates various functional groups, and the corresponding reduced heterocycles can be obtained in high yields. Experimental studies indicate a metal-ligand cooperative catalysis mechanism.

Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis.

Herein, the first acceptorless dehydrogenation of tetrahydroquinolines (THQs), indolines, and other related N-heterocycles, by merging visible-light photoredox catalysis and cobalt catalysis at ambient temperature, is described. The potential applications to organic transformations and hydrogen-storage materials are demonstrated. Primary mechanistic investigations indicate that the catalytic cycle occurs predominantly by an oxidative quenching pathway.

Acceptorless dehydrogenation of N-heterocycles by supported Pt catalysts

Pt metal nanoparticles loaded on various supports and carbon-supported various metal catalysts are tested for dehydrogenation of 6-methyl-1,2,3,4- tetrahydroquinoline to 6-methyl-quinoline under oxidant-free conditions. In the 20 types of the catalysts screened, carbon-supported Pt catalyst (Pt/C) shows the highest activity. Pt/C is reusable after the reaction and is effective for dehydrogenation of various N- heterocycles (tetrahydroquinolines and indoline). Pt/C is also effective for hydrogenation of quinoline under 3bar H2. The results demonstrate that this catalytic method may be useful for an organic hidride–based hydrogen storage system.