Abstract

This work describes the synthesis and evaluation as catalysts of two ruthenium(II) complexes, RuC1 and RuC2, containing NPN ligands=(N-(phenyl(pyridin-2-ylamino)phosphino)pyridin-2-amine and 2-((phenyl(pyridin-2-ylmethyl)phosphino)methyl)pyridine, respectively) for furfural and hydroxymethylfurfural hydrogenation. The catalysts displayed exceptional activity under mild conditions (180 °C, 40 bar H2) achieving over 98 % conversion and 98–99 % selectivity towards furfuryl alcohol (from furfural) and bis(hydroxymethyl)furan (from hydroxymethylfurfural) within 30 min, using a substrate-catalyst ratio of 3000:1. Remarkably, the catalysts maintained their efficacy even at a tenfold higher substrate loading (10,000:1), albeit with extended reaction times (3 and 4 h for furfural and hydroxymethylfurfural, respectively). Turnover frequencies (TOFs) were impressive, reaching 3920 h?1 and 3200 h?1 for furfural hydrogenation with the catalyst RuC1 and RuC2, respectively. Similarly, TOFs for hydroxymethylfurfural hydrogenation were 2450 h?1 and 2475 h?1 for RuC1 and RuC2, respectively. Notably, the catalysts exhibited excellent stability under reaction conditions. These findings demonstrate the promising potential of RuC1 and RuC2 for efficient hydrogenation of biomass-derived furans, offering a sustainable approach for the production of valuable bio-based chemicals. © 2024