title: Syntheses and reactivities of stable halosilylenoids, (Tsi)X2SiLi (Tsi=C(SiMe3)3, X=Br, Cl).
abstract: 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.
authors.affiliation: Department of Chemistry, Graduate School, Yonsei University, Seoul 120-749, South Korea. melee@dragon.yonsei.ac.kr
authors.forename: Myong Euy
authors.initials: ME
authors.lastname: Lee
authors.forename: Hyeon Mo
authors.initials: HM
authors.lastname: Cho
authors.forename: Young Mook
authors.initials: YM
authors.lastname: Lim
authors.forename: Jin Kyong
authors.initials: JK
authors.lastname: Choi
authors.forename: Chang Hee
authors.initials: CH
authors.lastname: Park
authors.forename: Seong Eun
authors.initials: SE
authors.lastname: Jeong
authors.forename: Uk
authors.initials: U
authors.lastname: Lee