Reactivity of (TMS)₂N(η¹‑Cp*)SiSi(η¹‑Cp*)N(TMS)₂ toward the Halides of Groups 13–15

In this paper, we have demonstrated the unique reactivity of a previously reported disilene [(TMS)₂N­(η¹-Me₅C₅)­SiSi­(η¹-Me₅C₅)­N­(TMS)₂] (1) with the halides of groups 13–15, which resulted in the formation of silicon–E (E = B, Al, Ge, P) bonds. Treatment of 1 with Lewis acidic BCl₃ led to the formation of a cationic boron species [Cp*BSi­(Cl)₂N­(TMS)₂)]­[BCl₃SiCl₃] (2). In contrast, the reaction of 1 with BCy₂Cl afforded an oxidative addition product [(TMS)₂N­(η¹-Me₅C₅)­Si­(BCy₂)­(Cl)] (3) via the insertion of a Si­(II) atom into the B–Cl bond. Extending the reaction with its higher congener led to classical Lewis acid-base adducts, (TMS)₂N­(η¹-Me₅C₅)­Si→AlCl₃ (4) and (TMS)₂N­(η¹-Me₅C₅)­Si→AlBr₃ (5), respectively. The reaction of GeCl₂ with 1 proceeded in a completely different manner and resulted in a hybrid dendrimeric compound [HGe­(Si­(Cl)₂N­(TMS)₂)₃] (6), whereas, with SnCl₂, it led to Cp*SnCl (7). Lastly, the reaction of Ph₂PCl followed the same pattern like Cy₂BCl and led to the formation of an oxidative addition product [(TMS)₂N­(η¹-Me₅C₅)­Si­(PPh₂)­(Cl)] (9) with a Si–P bond.