Green One-Pot Synthesis of Benzimidazoles from Dinitroarenes in Water Using a Ru-Doped Co-Based Heterogeneous Catalyst

[EN] A novel methodology is presented for preparing non-noble metal-based heterogeneous catalysts doped with low amounts of noble metals, yielding highly active and reusable materials for sustainable organic transformations. A new Co-Ru@C catalyst was developed by incorporating small ruthenium nanop...

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Detalles Bibliográficos
Autores: del Río-Rodríguez, Jose Luis, Molina, Maria Asunción, Costley-Wood, Lucy, Falcini, Chiara, Beale, Andrew M., Gutiérrez-Tarriño, Silvia, Oña-Burgos, Pascual|||0000-0002-2341-7867
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/228461
Acceso en línea:https://riunet.upv.es/handle/10251/228461
Access Level:acceso abierto
Palabra clave:1,2-dinitroarenes
Benzimidazoles
Cobalt carbon catalysts
Heterogeneous catalysis
Hydrogenative coupling
One-pot reactions
Ruthenium doping
Descripción
Sumario:[EN] A novel methodology is presented for preparing non-noble metal-based heterogeneous catalysts doped with low amounts of noble metals, yielding highly active and reusable materials for sustainable organic transformations. A new Co-Ru@C catalyst was developed by incorporating small ruthenium nanoparticles (1 wt %) and cobalt nanoparticles (10 wt %) on Vulcan carbon via pyrolysis of a ruthenium-doped cobalt metal-organic framework supported on carbon (2D-Co(Ru)MOF/C). Advanced characterization (in situ PXRD and XAS, HAADF-STEM, HRTEM) confirmed strong Co-Ru interactions, enhancing catalytic activity. The catalyst was evaluated in the one-pot reductive amination of dinitrobenzenes to benzimidazoles using molecular hydrogen and water, which is in line with green chemistry. The synergistic effect between Co and Ru enabled quantitative product yields under significantly milder reaction conditions than the existing ones. In addition, ruthenium was found to facilitate hydrogen activation in the bimetallic material compared with its undoped Co@C counterpart. Regarding stability, the Co-Ru@C catalyst retained its activity over at least five consecutive cycles without metal leaching or structural degradation. This material demonstrated a broad substrate scope, affording over 20 functionalized benzimidazoles in high yields. Half-gram-scale syntheses of commercial Diabazole and Fuberidazole further validated the scalability of this approach.