Aluminyl derived ethene functionalization with heteroallenes, leading to an intramolecular ligand rearrangement

Abstract

The aluminacyclopropane K[Al(NON)(η-C₂H₄)] ([NON]²⁻ = [O(SiMe₂NDipp)₂]²⁻, Dipp = 2,6-iPr₂C₆H₃) reacts with CO₂ and iPrNCNiPr to afford ring-expanded products of C–C bond formation. The latter system undergoes a 1,3-silyl retro-Brook rearrangement of the NON-group, to afford the [NNO]²⁻ ligand ([NNO]²⁻ = [N(Dipp)SiMe₂N(Dipp)SiMe₂O]²⁻). The mechanism of transformation was examined by density functional theory (DFT).