Hydrogenolysis of Polysilanes Catalyzed by Low‐Valent Nickel Complexes

The dehydrogenation of organosilanes (R_xSiH_4?x) under the formation of Si?Si bonds is an intensively investigated process leading to oligo‐ or polysilanes. The reverse reaction is little studied. To date, the hydrogenolysis of Si?Si bonds requires very harsh conditions and is very unselective, leading to multiple side products. Herein, we describe a new catalytic hydrogenation of oligo‐ and polysilanes that is highly selective and proceeds under mild conditions. New low‐valent nickel hydride complexes are used as catalysts and secondary silanes, RR′SiH₂, are obtained as products in high purity.