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

Andrea O'Reilly; Michael G Gardiner; Claire L McMullin; J Robin Fulton; Martyn P Coles

doi:10.1039/d3cc05785b

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

Chem Commun (Camb). 2024 Jan 18;60(7):881-884. doi: 10.1039/d3cc05785b.

Authors

Andrea O'Reilly¹, Michael G Gardiner², Claire L McMullin³, J Robin Fulton¹, Martyn P Coles¹

Affiliations

¹ School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6012, New Zealand. martyn.coles@vuw.ac.nz.
² Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia.
³ Department of Chemistry, University of Bath, Bath, BA2 7AY, UK. cm2025@bath.ac.uk.

PMID: 38165276
DOI: 10.1039/d3cc05785b

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).