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 reaction of Cu(I) bisguanidine complexes with nitric oxide and the formation of intermediate species were monitored via UV-vis spectroscopy at low temperature, with the occurrence of characteristic absorption bands. The origin of the emerging species and their character were substantiated by electron paramagnetic resonance (EPR) measurements and density functional theory (DFT) studies showing a delocalized {CuNO} 11 radical species. Furthermore, this system was transferred to the SuperFocus mixer setup, which allows rapid mixing and the determination of decay constants at ambient temperatures of the thermally sensitive species. However, these experiments demonstrated the limits of these systems, such as the NO saturation in organic solvents and a preferably precise temperature control within the SuperFocus mixer, which should be addressed in the future.