Catalytic Hydrogenation of Arenes in Water Over In Situ Generated Ruthenium Nanoparticles Immobilized on Carbon

Abstract

We describe a tandem process to generate active Ru nanoparticles (≈7 nm) immobilised in situ on carbon from an organometallic precursor and formic acid to afford the hydrogenation of a wide range of arenes and heteroarenes in yields up to 72 % with high conversions and selectivities for the desired products. The hydrogenation of several substrates analogous to lignin‐derived fragments to the corresponding alicyclic products was also achieved. Our experimental investigations evidenced that the observed enhanced activity for arene hydrogenation was driven by the unique structural advantages of the organometallic precursor to activate formic acid, in which the presence of a nitrogen ligand is crucial to achieve a high catalytic activity. TEM analysis revealed the formation of Ru0 nanoparticles, and Hg0 poisoning experiments support the heterogeneous nature of the active catalyst.

Low-temperature hydrogen production from methanol over a ruthenium catalyst in water

“…The literature revealed that the reaction performed under reducing conditions may result in the transformation of the organometallic Ru precursor into Ru(0) nanoparticles. [39][40][41][42][43] Chaudret et al established the mechanism and the process for the transformation of organometallic ruthenium complexes into Ru nanoparticles. 42,43 Similarly, some other groups have also established the transformation of organometallic ruthenium complexes into Ru nanoparticles.…”

N‐Heterocyclic Carbene (NHC)‐Stabilized Ru0 Nanoparticles: In Situ Generation of an Efficient Transfer Hydrogenation Catalyst

“…[14][15][16] Most nanoparticulate catalysts are bests tabilized by surfactants,s olvents,o rl igands, which provide stabilityb yb inding to the metal surface. [10,[17][18][19][20] As the catalytic properties of MNPs are strongly influencedb yt heir surface state, [21,22] many N, S, P, and C-based ligands have been used to control the size of NPs and tune the stereoelectronic properties of the surface. It is not surprising then, that N-heterocyclic carbenes (NHCs), which have emerged as ligandsp ar excellence in organometallics, [23] have found utility in stabilizing MNPs.…”

Synthesis of Functional Chemicals from Lignin‐derived Monomers by Selective Organic Transformations

“…[62] For example, Huang et al have shown a well-defined phenanthroline-based PN 3 À Ru pincer based complex can efficiently catalyze the hydrogenation of lignin-derived phenols (Scheme 30). [62] In addition, Singh and co-workers [63] synthesized η 6 -arene-ruthenium complexes and used them for the reduction of ligninderived fragments in presence of formic acid and water to afford the corresponding aliphatic cyclic compounds in good yields.…”