Pavel S. Yaremov

This study aimed to develop new catalysts, based on MoS₂, for the hydrogenation of bromoquinolines without C-Br bond cleavage. The mechanochemical exfoliation of the bulk MoS₂ in the presence of NaCl resulted in the formation of the material (MoS₂-1), consisting of flat plates of size between ca. 40 × 100 and ca. 250 × 400 nm². Similar grinding of MoS₂ in the presence of NH₄Cl produced smaller nanoplates of size between ca. 10 × 30 and ca. 50 × 300 nm² (MoS₂-2). These materials were characterized using powder XRD, TEM, SEM, Raman spectroscopy and XPS. The specific surface area of the MoS₂-1 and MoS₂-2 samples was estimated using the analysis of N₂ adsorption isotherms. Both materials were catalytically active in the hydrogenation of quinoline; 1,2,3,4-tetrahydroquinoline (THQ) was the sole product and its yield grew proportionally to the accessible surface area of the catalyst. The hydrogenation of 5- and 8-bromoquinolines in the presence of MoS₂-1 and MoS₂-2 led to the respective bromo-THQs with almost quantitative yields, while the hydrogenation of 6-bromoquinoline resulted in the formation of the respective 6-bromo-THQ with the yield up to 30%. In the case of 7-bromoquinoline, N-methylated 7-bromo-THQ was formed almost quantitatively.

A series of composites containing nanoparticles of NiO (from 1 to 10% by weight per Ni), deposited on NORIT charcoal, was prepared by the decomposition of the Ni⁰ complex Ni(cod)₂ (cod = cis,cis-1,5-cyclooctadiene). Ni content in the composites was set by loading the appropriate quantities of the Ni(cod)₂ precursor. The catalytic activity of the composites was associated with the in situ generation of active sites due to a reduction in NiO, hence the composites could be stored in air without a loss in their catalytic performance. The composites were analyzed by powder XRD, TEM, XPS, and adsorption methods. The hydrogenation of quinoline was used as a reference reaction for studies of the influence of temperature, P(H₂), catalyst loading on the product yield, and for the selection of the composite possessing the highest performance. It was found that 3% Ni loading was the most optimal. This composite was used as an efficient catalyst for the hydrogenation of compounds with ethylene and acetylene bonds, nitro- and keto- groups as well as a series of substituted quinolines and analogs. The studied composites can be proposed as air-stable and efficient catalysts for the hydrogenation of a wide range of organic compounds.