Flash Communication: Access to a Chloro Substituted Zinciooctasilane through Controlled Si–H Activation

Abstract Oligosilanes are attractive precursors for advanced silicon materials, yet efficient routes beyond monosilanes remain limited. We demonstrate that the nonachloro-isotetrasilane undergoes highly selective Si–H activation with an organozinc reagent. The directed zincation defines a metal-controlled platform for the preparation of functional oligosilanes, offering new opportunities in the polysilicon precursor design and silicon nanostructure synthesis. For comparison, the literature-known mercuriooctasilane was also prepared, and both compounds were structurally characterized. Interestingly, these silylmetal compounds exhibit divergent photochemistry: mercury enables clean Si–Si bond formation, whereas zinc coordination effectively blocks radical pathways.