Hydrogenolysis of Polysilanes Catalyzed by Low‐Valent Nickel Complexes

The dehydrogenation of organosilanes (R x SiH 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′SiH 2 , are obtained as products in high purity.