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 -CH2OH 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.

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Novel rhodium(i) complexes [RhCl(NBD)(NHC)] [NHC = 1-benzyl-3-R-imidazolin-2-ylidene; R = Me, Bz, Tr, tBu]: determination of the rotation barriers about the Rh-carbene and catalytic activity in the hydrosilylation of terminal alkynes.

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