Syntheses and Reactivities of Stable Halosilylenoids, (Tsi)X 2 SiLi (Tsi=C(SiMe 3 ) 3 , X=Br, Cl)

Halosilylenoids, stable at room temperature (Tsi)X 2 SiLi (Tsi=C(SiMe 3 ) 3 , X=Br, Cl), were synthesized from the reaction of TsiSiX 3 with lithium naphthalenide. Bromosilylenoid reacted with t BuOH and MeI both at −78 °C and at room temperature to give (Tsi)HSiBr 2 and (Tsi)MeSiBr 2 , respectively, in high yields; this clearly shows its nucleophilicity. In the reaction of bromosilylenoid with methanol, 2‐propanol, and 2,3‐dimethyl‐1,3‐butadiene, the corresponding products, (Tsi)HSi(OMe) 2 , (Tsi)HSi(O i Pr)Br, and bromo(Tsi)silacyclopent‐3‐ene, were obtained in high yields; this demonstrates its amphiphilic property, as if bromosilylene would be trapped. Chlorosilylenoid also exhibited both nucleophilic and amphiphilic properties. The 29 Si chemical shifts for (Tsi)Br 2 SiLi, (Tsi)Br 2 SiK, and (Tsi)Cl 2 SiLi were 106, 70, and 87 ppm, respectively.