A family of crystalline lithium anilide solvates, [{PhN(H)Li·(pyr)2}2] 1, [{PhN(H)Li·(4-Me-pyr)2}2] 2 and [{PhN(H)Li}4·(4-But-pyr)6] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane–toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N–Li]2 ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N–Li]2 transoid ring, separating two mixed ligand [(anilido)N–Li-(pyr)N–Li] rings, made possible by the unusual μ-bonding of a 4-tert-butylpyridine ligand. A combination of 1H, 7Li and 13C NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [2H8]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300–193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.
You have access to this article
Please wait while we load your content...
Something went wrong. Try again?