Reactivity of (TMS) 2 N(η 1 ‑Cp*)SiSi(η 1 ‑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) 2 N­(η 1 -Me 5 C 5 )­SiSi­(η 1 -Me 5 C 5 )­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 BCl 3 led to the formation of a cationic boron species [Cp*BSi­(Cl) 2 N­(TMS) 2 )]­[BCl 3 SiCl 3 ] ( 2 ). In contrast, the reaction of 1 with BCy 2 Cl afforded an oxidative addition product [(TMS) 2 N­(η 1 -Me 5 C 5 )­Si­(BCy 2 )­(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) 2 N­(η 1 -Me 5 C 5 )­Si→AlCl 3 ( 4 ) and (TMS) 2 N­(η 1 -Me 5 C 5 )­Si→AlBr 3 ( 5 ), respectively. The reaction of GeCl 2 with 1 proceeded in a completely different manner and resulted in a hybrid dendrimeric compound [HGe­(Si­(Cl) 2 N­(TMS) 2 ) 3 ] ( 6 ), whereas, with SnCl 2 , it led to Cp*SnCl ( 7 ). Lastly, the reaction of Ph 2 PCl followed the same pattern like Cy 2 BCl and led to the formation of an oxidative addition product [(TMS) 2 N­(η 1 -Me 5 C 5 )­Si­(PPh 2 )­(Cl)] ( 9 ) with a Si–P bond.