Transformation of the bis(trimethylsilyl)methyl into aza-allyl and β-diketinimato ligands; the X-ray structures of [Li{N(R)C(But)CH(R)}]2 and [Zr{N(R)C(But)CHC(Ph)N(R)}Cl3](R = SiMe3)

Abstract

The reaction of LiCHR₂ with Bu^tCN gives the η³-aza-allyl [[graphic omitted]′)]₂1, which in turn affords (i) the aza-allyls [{[graphic omitted]′)}_n](with KOBu^t), rac-[[graphic omitted]′)₂Cl₂](with ZrCl₄) and [[graphic omitted](H)CH(R)Buⁿ}]₂, (with successively CH₂Br₂ and LiBuⁿ), (ii) the β-diketinimates [[graphic omitted]‴)Cl₃](M = Zr 4 or Hf, via MCl₄) and [[graphic omitted]‴)]₂(with 2PhCN), and (iii) the imine RCH₂C(Bu^t): NR (with H₂O); X-ray data are provided for 1 and 4[LL′= N(R)C(Bu^t)CHR, L″L‴= N(R)C(Bu^t)C(H)C(Ph)NR; R = SiMe₃].