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 iPrNCNiPr 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).