Insertion reactions involving a triamidoamine-supported zirconium complex

Abstract

The reactivity of a triamidoamine-supported zirconium complex, [κ⁵-N,N,N,N,C-(Me₃SiNCH₂CH₂)₂NCH₂CH₂NSiMe₂CH₂]Zr (1), toward polar, small-molecule substrates including isocyanides, organic azides, carbodiimides, nitriles, and ketones has been explored. The small-molecule substrates were found to react with the Zr–C bond of complex 1via 1,1- or 1,2-insertion modes, affording ring-expanded products containing new zirconium–carbon, zirconium–nitrogen, or zirconium–oxygen bonds. Solid-state structures of a 1,1-insertion product [κ⁶-N,N,N,N,N,N-(Me₃SiNCH₂CH₂)₂NCH₂CH₂NSiMe₂CH₂N(NNCH₂Ph)]Zr (3) and a 1,2-insertion product [κ⁵-N,N,N,N,O-(Me₃SiNCH₂CH₂)₂NCH₂CH₂NSiMe₂CH₂CPh₂O]Zr (5) are reported.