The reactions of lithium trimethysilylmethyls with isocyanides; structures and reactions of the derived lithium 1-azaallyls, β-diketiminates and a 1-azabuta-1,3-dienyl-3-amide
Abstract
The insertion of ArNC (Ar = 2,6-Me2C6H3) or ButNC into the Li–C bond of [Li{C(H)(R)R′}] (R = SiMe3, R′ = R or Ph) led to (i) the lithium 1-azaallyls [Li{N(R″)C(R)C(H)R′}(tmen)] (6a R′ = R, R″ = Ar; 6b R′ = Ph, R″ = Ar; 6c R′ = Ph, R″ = But), (ii) the lithium β-diketiminates [Li{N(But)C(R)C(H)C(R)NBut}][(LiCHR2)(CNBut)] 1, Li{N(Ar)C(R)C(H)C(R)N(Ar)}
2 and [Li{N(Ar)C(R)C(H)C(Ph)N(R)}(tmen)] 7 (from 6a and PhCN), or (iii) the lithium amide [Li{N(Ar)C(R)C[N(Ar)]C(H)Ph}(tmen)] 8. Treatment of the lithium β-diketiminates 1 and 2 with ZrCl4 yielded the complexes [ZrCl3{N(But)C(R)C(H)C(R)NBut}] 3 or [Zr{N(Ar)C(R)C(H)C(R)N(Ar)}Cl2(μ-Cl)2Li(OEt2)2] 4, while reaction of the lithium compounds 2 or 8 with