Hydrogenolysis of Polysilanes Catalyzed by Low-Valent Nickel Complexes

The dehydrogenation of organosilanes (RxSiH4-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.