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

The aluminacyclopropane K[Al(NON)(η-C 2 H 4 )] ([NON] 2- = [O(SiMe 2 NDipp) 2 ] 2- , Dipp = 2,6-iPr 2 C 6 H 3 ) reacts with CO 2 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)SiMe 2 N(Dipp)SiMe 2 O] 2- ). The mechanism of transformation was examined by density functional theory (DFT).