Syntheses and reactivities of stable halosilylenoids, (Tsi)X2SiLi (Tsi=C(SiMe3)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 tBuOH and MeI both at -78 degrees 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(OiPr)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.