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Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Adhwa Alharbi, Dr Corinne Wills, Dr Casey Dixon, Dr Chuan ChengORCiD, Dr Fernando Russo AbegaoORCiD
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Ruthenium nanoparticles stabilised by an amine-modified Ordered Mesoporous Silica Immobilized Ionic Liquid (OMSIIL) catalyses the partial reduction of nitrobenzene to 1,2-diphenylhydrazine with 100% selectivity as well as the complete reduction to aniline. High selectivity for the partial reduction of nitrobenzene to 1,2-diphenylhydrazine 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 1,2-diphenylhydrazine using a ruthenium nanoparticle-based catalyst. Moreover, the initial TOF of 320 mol nitrobenzene converted mol Ru-1 h-1 for the partial reduction of nitrobenzene to 1,2-diphenylhydrazine 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.
Author(s): Doherty S, Knight JG, Alharbi Adhwa, Wills C, Dixon C, Cheng Chuan, Russo-Abegao Fernando, Chamberlain TW, Yan Han, Griffiths Anthony, Bourne Richard, Collins Sean, Wu Kejun, Alshaikh H
Publication type: Article
Publication status: Published
Journal: ChemCatChem
Year: 2024
Pages: Epub ahead of print
Online publication date: 07/03/2024
Acceptance date: 07/03/2024
Date deposited: 07/03/2024
ISSN (print): 1867-3880
ISSN (electronic): 1867-3899
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
URL: https://doi.org/10.1002/cctc.202400013
DOI: 10.1002/cctc.202400013
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