Reactions of silylallyl-lithium or -potassium compounds with ButCN; synthesis and structures of [M{N(SiMe2R)C(But)(CH)3SiMe2But}] [M = Li(tmen), R = Me; or M = K, R = But], [Li{N(SiMe3)C(But)>>CCHC(SiMe3)(CH2)2C>>H2}(tmen)] and [{Li[NC(But)>>CHCHC(SiMe3)(CH2)2C>>H2]}4] (tmen = Me2NCH2CH2NMe2)

Abstract

The reactions of a 1,3-bis(silyl)allyl-lithium-tmen or corresponding potassium reagent with Bu^tCN yielded the appropriate silyl migration product [Li{N(SiMe₂R¹)C(Bu^t)(CH)₃SiMe₂R²}(tmen)] (R¹ = R² = Bu^t, R¹ = Me, R² = Bu^t or R¹ = R² = Me), [Li{N(SiMe₃)C(Bu^t)CCHC(SiMe₃)(CH₂)₂CH₂}(tmen)] or [K{η⁴-N(SiMe₂R¹)C(Bu^t)(CH)₃SiMe₂R²}] (R¹ = R² = Bu^t, R¹ = Bu^t, R² = Me or R¹ = R² = Me). The 1,5-bis(silyl)-1-azapenta-2,4-dienyllithium tmen-free analogues were obtained by lithiation of the corresponding enamines. The reaction of 2-trimethylsilylcyclohexenyllithium with Bu^tCN produced the imidolithium complex [{Li[NC(Bu^t)CHCHC(SiMe₃)(CH₂)₂CH₂]}₄]. Single crystal structures of four complexes have been determined.