Lithium and aluminium carbamato derivatives of the utility amide 2, 2, 6, 6- tetramethylpiperidide

Insertion of CO2 into the metal-N bond of a series of synthetically-important alkali-metal TMP (2,2,6,6-tetramethylpiperidide) complexes has been studied. Determined by X-ray crystallography, the molecular structure of the TMEDA-solvated Li derivative shows a central 8-membered (LiOCO)2 ring lying in a chair conformation with distorted tetrahedral lithium centres. While trying to obtain crystals of a THF solvated derivative, a mixed carbonato/carbamato dodecanuclear lithium cluster was formed containing two central (CO3)2- fragments and eight O2CTMP ligands with four distinct bonding modes. A bisalkylaluminium carbamato complex has also been prepared via two different methods (CO2 insertion into a pre-formed Al-N bond and ligand transfer from the corresponding lithium reagent) which adopts a dimeric structure in the solid state.