A Neutral Silicon(II) Half-Sandwich Compound

Metathesis reaction of a dilithio borole dianion, a cyclic π-ligand isoelectronic to ubiquitous cyclopentadienyls, with two equivalents of "silicocenium" cation [Cp*Si]⁺ as a source of low-valent Si(II), cleanly gives a borole half-sandwich π-complex of Si(II) and silicocene. The resulting half-sandwich complex is a neutral isoelectronic analogue to the iconic silicocenium cation and features the rare structural motif of an apical silicon(II) atom with an energetically high lying lone pair of electrons that is shown to be accessible for coordination chemistry toward tungsten carbonyl. Protonation at the Si(II) atom with [H(OEt₂)₂][Al{OC(CF₃)₃}₄] induces formal oxidation, and the compound rearranges to incorporate the Si atom into the carbocyclic base to give an unprecedented cationic 5-sila-6-borabicyclo[2.1.1]hex-2-ene. This rearrangement is accompanied by drastic changes in the ¹¹B and ²⁹Si NMR chemical shifts.