Lithium dimethyl(amido)zinc complexes: contrasting zincate (amido = tmp) and inverse zincate (amido = hmds) structures on addition of TMEDA

Introducing TMEDA to the lithium dimethyl(amido)zincates 'LiZn(NR2)Me2' leads to a discrete ion-contacted zincate with TMEDA bound to lithium in the case of NR2 = TMP but to a novel 'inverse zincate' with TMEDA bound to zinc in the case of NR2 = HMDS, where unexpectedly Me2Zn(TMEDA) functions as a η1,μ ligand to dimeric (LiHMDS)2 molecules to afford a zigzag chain polymer