Substrate and product role in the Shvo's catalyzed selective hydrogenation of the platform bio-based chemical 5-hydroxymethylfurfuralElectronic supplementary information (ESI) available. CCDC 953038. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt00304g

The bio-based substrate and target product 2,5-bishydroxymethylfuran (BHMF) demonstrated to influence the reaction kinetics in the homogeneous reduction of 5-hydroxymethylfurfural (HMF) catalyzed by the Ru-based Shvo's catalyst. A combined experimental and computational study supports an important role of the -CH 2 OH moiety which may be involved in the catalytic cycle toward the formation of different intermediates from HMF and BHMF. The reaction is selective and leads to quantitative formation of BHMF working under mild conditions. Furthermore, an optimized recycling procedure which avoids the use of water, allows recover and reuse of the catalyst without loss of activity. The mechanistic insights from this work may be extended to provide a general description of the chemistry of the Shvo's catalyst feeding further bio-based molecules. The Shvo's catalyzed selective hydrogenation of HMF to BHMF showed substrate and product effects on the reaction rate. DFT calculation suggested the formation of several intermediates influencing the catalytic cycle.