The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigation to clarify the preferences of these metal species with respect to the activation of Si-H and/or Si-Si bonds remain elusive. Here, we report that platinum(0) species that bear isocyanide orN-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph2(H)SiSiPh2SiPh2Si(H)Ph2in a stepwise manner, whereby the Si-Si bonds remain intact. In contrast, analogous palladium(0) species are preferably inserted into the Si-Si bonds of the same linear tetrasilane, whereby the terminal Si-H bonds remain intact. Substitution of the terminal hydride groups in Ph2(H)SiSiPh2SiPh2Si(H)Ph2with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt4cluster.