Abstract: | tert‐Butyl(dichloromethyl)bis(trimethylsilyl)silane ( 4 ), prepared by the reaction of tert‐butylbis(trimethylsilyl)silane with trichloromethane and potassium tert‐butoxide, reacted with 2,4,6‐triisopropylphenyllithium (TipLi) (molar ratio 1 : 2) at room temperature to give (after hydrolytic workup) the silanol tBu(2,4,6‐iPr3C6H2)Si(OH)–CH(SiMe3)2 ( 15 ). The formation of 15 is discussed as proceeding through the indefinitely stable silene tBu(2,4,6‐iPr3C6H2)Si=C(SiMe3)2 ( 13 ), but attempts to isolate the compound failed. Treatment of (dibromomethyl)ditert‐butyl(trimethylsilyl)silane ( 7 ), made from tBu2(Me3Si)SiH, HCBr3 and KOtBu, with methyllithium (1 : 3) at –78 °C afforded tBu2MeSi–CHMeSiMe3 ( 19 ); 7 and phenyllithium (1 : 3) under similar conditions gave tBu2PhSi–CH2SiMe3 ( 20 ). The reaction paths leading to 15 , 19 and 20 are discussed. Reduction of 7 with lithium in THF produced the substituted ethylene tBu2(Me3Si)SiCH=CHSitBu2SiMe3 ( 21 ). For 21 the results of an X‐ray structural analysis are given. |