LAUSR

Herein, we describe the facile and selective one-pot synthetic route to silylene-aluminum and silylene-gallium adducts. Reduction of silylene LSiCl (L = PhC(NtBu)2) with KC8 in the presence of bulky and sterically hindered cyclopentadienyl aluminum Cp'''AlCl2 (Cp''' = 1,2,4-tBu3C5H2) and gallium [η1-Cp'''Ga(μ-Cl)Cl]2 to afford the Lewis acid-base adducts η1-Cp'''M(Cl2) ← Si(L)-SiL (M = Al, 1; M = Ga, 3). To confirm the formation of the Lewis acid-base adduct, the bis(silylene) LSi(I)-Si(I)L reacts with Cp'''AlI2 to form η1-Cp'''Al(I2) ← Si(L)-SiL (2). These are the first examples where one Si atom in the bis(silylene) is a Lewis base and coordinates with aluminum or gallium to form a Lewis acid-base adduct, while the other Si atom in the bis(silylene) still maintains the characteristics of silylene. Compound 3 was heated to 70 °C in toluene for 4 hours and decomposed into the silylene LSiCl and Cp'''GaI. Compounds 1-3 are well characterized with NMR spectroscopic methods and single-crystal X-ray structural analysis.