Selective Partial Reduction of Nitroarenes to the Hydrazoarene Catalyzed by Amine‐Modified Ordered Mesoporous Silica Immobilized Ionic Liquid (OMSIIL) Stabilised RuNPs.

Ruthenium nanoparticles stabilised by an amine‐modified Ordered Mesoporous Silica Immobilized Ionic Liquid (OMSIIL) are efficient catalysts for the partial reduction of nitrobenzene to hydrazobenzene with 100 % selectivity as well as the complete reduction to aniline. High selectivity for the partial reduction of nitrobenzene to hydrazobenzene was obtained when the reaction was conducted in ethanol with 0.5 mol% catalyst and NaBH4 as the hydrogen donor whereas aniline was obtained as the sole product in water when dimethylamine borane (DMAB) was used as the hydrogen donor. Interestingly, while a range of electron poor nitroarenes were reduced to the corresponding hydrazoarene with high selectivities and good conversions, nitroarenes substituted with electron donating groups resulted in complete reduction to the aniline. Composition‐time profiles suggest that reductions conducted in ethanol with sodium borohydride occur via the condensation pathway while those conducted in water using dimethylamine borane as the hydrogen source may well go via the direct pathway. This is the first example of the selective reduction of nitrobenzene to hydrazobenzene using a ruthenium nanoparticle‐based catalyst and the initial TOF of 320 mol nitrobenzene converted mol Ru−1 h−1 for the partial reduction of nitrobenzene to hydrazobenzene is markedly higher than previous literature reports. A study of the catalyst performance as a function of the surface modification revealed that each component has a direct and dramatic effect on the efficacy as RuNPs stabilised by COK‐12 modified with imidazolium‐based ionic liquid and a primary amine gave the highest conversion while selective removal of either component or replacement of the primary amine with a tertiary amine resulted in a marked reduction in efficiency. [ABSTRACT FROM AUTHOR]