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

Abstract

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.