New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide

The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA·Na(µ-TMP)(µ-iBu)Al(iBu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2·Na(µ-CCPh)(µ-iBu)Al(iBu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(O)N(iPr)2}·Li{2-[1-C(O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium