Polysilane‐Supported Nickel as an Efficient Catalyst for the Hydrogenation of Aromatic Compounds †

Comprehensive Summary The treatment of poly(monohydro)silane with the zero‐valent nickel precursor Ni(cod) 2 (cod = 1,5‐cyclooctadiene) in toluene at 100 °C leads to the formation of a heterogeneous Ni/Si catalyst that efficiently mediates the hydrogenation of various arenes and heteroarenes under reaction conditions that are relatively mild compared to conventional heterogeneous nickel‐based catalysts such as Raney nickel. For instance, the hydrogenation of benzene proceeds smoothly under 8 atm of H 2 (100 °C, 24 h) to exclusively afford cyclohexane in a quantitative yield. An X‐ray photoelectron spectroscopy (XPS) analysis revealed that the composition of this heterogeneous Ni/Si catalyst resembles that of nickel‐silicide, albeit that the present catalyst exhibits a catalytic activity that is significantly superior to that of commercially available nickel‐silicide. This heterogeneous Ni/Si catalyst can be recycled multiple times via simple centrifugation without any noticeable decrease in catalytic activity.