Bimetallic iron–ruthenium nanoparticles embedded in an acidic supported ionic liquid phase (FeRu@SILP+IL‐SO3H) act as multifunctional catalysts for the selective hydrodeoxygenation of carbonyl groups in aromatic substrates. The catalyst material is assembled systematically from molecular components to combine the acid and metal sites that allow hydrogenolysis of the C=O bonds without hydrogenation of the aromatic ring. The resulting materials possess high activity and stability for the catalytic hydrodeoxygenation of C=O groups to CH2 units in a variety of substituted aromatic ketones and, hence, provide an effective and benign alternative to traditional Clemmensen and Wolff–Kishner reductions, which require stoichiometric reagents. The molecular design of the FeRu@SILP+IL‐SO3H materials opens a general approach to multifunctional catalytic systems (MM′@SILP+IL‐func).

Catalytic hydrogenolysis of diaryl ethers is achieved by using ruthenium nanoparticles immobilized on an acidic supported ionic liquid phase (Ru@SILP-SO3H) as a multifunctional catalyst. The catalyst components are assembled through a molecular approach ensuring synergistic action of the metal and acid functions. The resulting catalyst is highly active for the hydrogenolysis of various diaryl ethers. For symmetric substrates such as diphenyl ether, hydrogenolysis is followed by full hydrodeoxygenation producing the corresponding cycloalkanes as the main products. For unsymmetric substrates, the cleavage of the C–O bond is regioselective and occurs adjacent to the unsubstituted phenyl ring. As hydrogenation of benzene is faster than hydrodeoxygenation over the Ru@SILP-SO3H catalyst, controlled mixtures of cyclohexane and substituted phenols are accessible with good selectivity. Application of Ru@SILP-SO3H catalyst in continuous-flow hydrogenolysis of 2-methoxy-4-methylphenoxybenzene is demonstrated with use of commercial equipment.

The synthesis, characterization, and catalytic properties of bimetallic cobalt‐rhodium nanoparticles of defined Co:Rh ratios immobilized in an imidazolium‐based supported ionic liquid phase (CoxRh100−x@SILP) are described. Following an organometallic approach, precise control of the Co:Rh ratios is accomplished. Electron microscopy and X‐ray absorption spectroscopy confirm the formation of small, well‐dispersed, and homogeneously alloyed zero‐valent bimetallic nanoparticles in all investigated materials. Benzylideneacetone and various bicyclic heteroaromatics are used as chemical probes to investigate the hydrogenation performances of the CoxRh100−x@SILP materials. The Co:Rh ratio of the nanoparticles is found to have a critical influence on observed activity and selectivity, with clear synergistic effects arising from the combination of the noble metal and its 3d congener. In particular, the ability of CoxRh100−x@SILP catalysts to hydrogenate 6‐membered aromatic rings is found to experience a remarkable sharp switch in a narrow composition range between Co25Rh75 (full ring hydrogenation) and Co30Rh70 (no ring hydrogenation).