Insertion of Ni(0) and Pd(0) precursors into the Si-Si bond of a disilane with two hypercoordinate silicon atoms.

The activation of the silicon-silicon bond in disilane Ph2Si(μ-PzMe2)2SiPh2 (1), which possesses two five-coordinate silicon centers, was achieved by a reaction with Pd(0) or Ni(0) precursors of modest steric demand to afford a dinuclear Pd complex (2) or two types of mononuclear Ni complexes (3 and 4), respectively.