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 or N-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph₂(H)SiSiPh₂SiPh₂Si(H)Ph₂ in 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)Ph₂ with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt₄ cluster.

过渡金属物种对有机硅化合物中 Si-H 键和/或 Si-Si 键的活化对于功能性有机硅化合物的生产起着至关重要的作用。尽管第 10 族金属物种经常用于激活 Si-H 和/或 Si-Si 键，但到目前为止，系统研究以阐明这些金属物种在激活 Si-H 和/或 Si- 方面的偏好硅键仍然难以捉摸。在这里，我们报告带有异氰化物或N -杂环卡宾 (NHC) 配体的铂 (0) 物种选择性地激活线性四硅烷 Ph ₂ (H)SiSiPh ₂ SiPh ₂ Si(H)Ph _{2的末端 Si-H 键}以逐步的方式，由此 Si-Si 键保持完整。相反，类似的钯 (0) 物质优选插入同一线性四硅烷的 Si-Si 键中，从而使末端 Si-H 键保持完整。用氯化物基团取代 Ph ₂ (H)SiSiPh ₂ SiPh ₂ Si(H)Ph ₂中的末端氢化物基团导致铂 (0) 异氰化物插入所有 Si-Si 键中，从而提供前所未有的之字形 Pt ₄簇。